Sie sind auf Seite 1von 11

Molecular Physics

An International Journal at the Interface Between Chemistry and


Physics

ISSN: 0026-8976 (Print) 1362-3028 (Online) Journal homepage: http://www.tandfonline.com/loi/tmph20

A tribute to Jan Erik Almlf

Hans P. Lthi & Trygve Helgaker

To cite this article: Hans P. Lthi & Trygve Helgaker (2017) A tribute to Jan Erik Almlf, Molecular
Physics, 115:17-18, 2033-2042, DOI: 10.1080/00268976.2017.1293305

To link to this article: http://dx.doi.org/10.1080/00268976.2017.1293305

Published online: 28 Jun 2017.

Submit your article to this journal

Article views: 64

View related articles

View Crossmark data

Full Terms & Conditions of access and use can be found at


http://www.tandfonline.com/action/journalInformation?journalCode=tmph20

Download by: [Chulalongkorn University] Date: 13 September 2017, At: 17:56


MOLECULAR PHYSICS,
VOL. , NOS. -,
https://doi.org/./..

MQM 2016

A tribute to Jan Erik Almlf


Hans P. Lthib and Trygve Helgakera
a
Department of Chemistry, Centre for Theoretical and Computational Chemistry (CTCC), University of Oslo, Oslo, Norway; b Laboratory of
Physical Chemistry, ETH Zrich, Zrich, Switzerland

ABSTRACT ARTICLE HISTORY


Received December
Accepted January

KEYWORDS
Computational quantum
Downloaded by [Chulalongkorn University] at 17:56 13 September 2017

chemistry; electronic
structure theory; molecular
properties; direct methods;
high performance
computing; chemical
modelling

1. The person University of Uppsala in 1974 with his thesis entitled:


Studies of Hydrogen Bonding by Quantum-Mechanical
Jan Erik Almlf (Figure 1) was born in Malung, a small
Calculations and X-ray Diffraction Methods.
community in the remote Dalarna region of central Swe-
After a short period with Enrico Clementi at IBM
den, on 1 April 1945. He received the degree of fil. kand.
Research Laboratory in San Jose, Jan Almlf accepted
(BA) at the University of Uppsala in Sweden in 1967
a position as associate professor (dosent) in theoretical
and graduated in 1971 from the same university with the
chemistry at the University of Oslo in Norway in 1976,
degree of fil. lic. (PhD), with a thesis on the crystal struc-
where he began a career of teaching and research in
tures of hydrates of perchloric acid, supervised by Prof.
computational physical chemistry, becoming professor of
I. Olavsson. Almlf s first publications appeared in 1971,
chemistry in 1982. In September 1985, he moved to the
when he published two experimental (X-ray) and two
University of Minnesota in Minneapolis as professor of
theoretical (extended-Hckel) papers.
chemistry and chemical physics where he was appointed
In 1968, Jan Almlf had visited the quantum-
a fellow of the Supercomputer Institute while continu-
chemistry group at the Department of Theoretical
ing his activities in research and teaching. He taught both
Physics at the University of Stockholm. Interactions with
undergraduate and graduate courses, and had 28 doctoral
Bjrn Roos, Per Siegbahn and Ulf Wahlgren thereby
and 16 post-doctoral research students. He also was one
brought Jan Almlf in contact with ab initio quantum
of the founding members of the biennial European Sum-
chemistry. The Stockholm group was working with the
mer School in Quantum Chemistry, directed by Bjrn
IBMOL code at the time. Inspired by this code but aim-
Roos and first held in August of 1989 in Tjrnarp (Swe-
ing to treat larger and more realistic systems, Jan Almlf
den) [3].
began to work on the MOLECULE integral code [1], with
Jan Almlf died on 16 January 1996, at the age of 50.
a unique point-group symmetry handling. Parts of the
He was survived by his wife Elisabeth and his children
code were debugged and tested at the Centre National
Anders, Mia and Martin. He was buried in Malung, his
de la Recherche Scientifique (CNRS) computer centre in
place of birth. To his honour, the American Chemical
Strasbourg as a visitor at the laboratory of Alain Veillards
Society held a symposium at its 1997 meeting in San
(see also acknowledgements in [1,2]). He received the
Francisco. The same year, Theoretical Chemistry
degree of fil. dr. (comparable to a Habilitation) at the

CONTACT Hans P. Lthi luethi@ethz.ch


Informa UK Limited, trading as Taylor & Francis Group
2034 H. P. LTHI AND T. HELGAKER

computation, Almlf writes: The calculations [136


contracted Gaussian functions]were performed with
the ab initio MO-LCGO-SCF method, using the for-
malism described by Roothaan. Using his MOLECULE
code [1,2] on the 360/195 computer of the San Jose
IBM Research Laboratory, with a theoretical peak per-
formance of approximately 5 Million Floating Point
Operations per Second (MFLOPS), a single-point cal-
culation took as little as 31 minutes for the electron
repulsion integrals and 6 seconds for each self-consistent
Figure . Jan Erik Almlf, April January . field (SCF) cycle. This performance was achieved by a
rigorous exploitation of molecular symmetry within a
Accounts published a Memorial Issue edited by Odd supermatrix formalism, reducing the number of integrals
Gropen, Bjrn Roos, Per Siegbahn, Peter R. Taylor to be stored from 170(unscreened) to 6 million, bringing
and Donald Truhlar [4]. This document lists all of his the disk-storage requirements to tractable size (in the
students and colleagues, and also shows his complete order of 100 MBytes).
Downloaded by [Chulalongkorn University] at 17:56 13 September 2017

bibliography.
2.2. Hitting the I/O wall and a change of paradigm
2. The scientist
While CPU power was steadily increasing, it became
apparent that input/output (I/O) would remain a bottle-
2.1. The early days: computation as an emerging
neck in ab initio calculations. Thus, when trying to repro-
tool in chemistry
duce the experimental structure of ferrocene and other
In quantum chemical research, a considerable fraction metallocenes using the HartreeFock method, the I/O
of the effort is devoted to improving the computational became the ultimate obstacle. In an attempt to harness
strategy. The work in this field can basically be charac- every single MByte of scratch space available, including
terised as aiming at a single goal: how can larger systems those on the system disk, to store the 11 million, two-
be made accessible to increasingly sophisticated meth- electron integrals on the University of Oslo CDC Cyber
ods? is the opening statement in an article contributed computer, a severe system crash ensued. Denied further
by Jan Almlf and Peter R. Taylor to the monograph access to the machine, the team was forced to reconsider
Advanced Theories and Computational Approaches to the situation [7].
the Electronic Structure of Molecules, edited by Clif- Indeed, inspired by a comment made by Enrico
ford E. Dykstra and published by the D. Reidel Pub- Clementi, his host at the San Jose IBM Research Lab-
lishing Company in 1984 [5]. Born into the world of oratory, Jan Almlf and co-workers Knut Fgri and
third-generation computers, with the ambition to explore Knut Korsell were at the time developing a prototype
chemistry on the basis of quantum-chemical methods, HartreeFock code that would build the Fock matrix
Jan Almlf recognised the tremendous potential of cur- from two-electron integrals as they were evaluated, avoid-
rent and future computing machineries early on. How- ing any external storage [8]. Running on a departmen-
ever, given the size and the complexity of the chemical tal Norwegian-built Norsk Data mini-computer (ND500)
problems that interested him, he also understood that, with a powerful CPU but limited I/O capabilities, the
in order to make these systems accessible to an increas- code needed to recompute the integrals in every SCF iter-
ingly sophisticated computational treatment, a consider- ation, putting the entire workload onto the CPU. Porting
able effort would have to be spent on implementation of a the code, later named Direct Self Consistent Optimiza-
method that is, mapping it on a given compute resource tion (DISCO) on the IBM 3033 main-frame computer of
(CPU, memory, external storage). the University of Zrich, it became possible to perform
One of Almlf s early papers as a single author, pub- HartreeFock calculations on ferrocene to the basis-set
lished in 1974 [6], reports the first ab initio calculation limit. In the largest computations, the wave function was
on the molecular and electronic structure of porphine expanded by more than 500 contracted basis functions
(Figure 2), a topic he would pursue throughout his [9], breaking the barrier of 255 functions set by eight-bit
career. The focus in his 1974 article is on the position integral addressing.
of the inner hydrogen atoms, with a comparison of The direct SCF method was a breakthrough an egg
computed N-H vibrational frequencies and computed of Columbus, marking the entry into a new paradigm
ionisation potentials with experiment. Regarding the and making new problems amenable to ab initio studies.
MOLECULAR PHYSICS 2035

Figure . The siren call of real chemistry: looking at porphin, the (unsubstituted) parent structure of all porphyrins.
Downloaded by [Chulalongkorn University] at 17:56 13 September 2017

screening of unimportant integrals became possible with


the direct SCF method. For large applications in extended
basis sets, the observed effective scaling was as low as
O(n2.2 ), much lower than the formal fourth-order scaling.
With the advent of larger memory systems, it made sense
to store two-electron integrals in memory, to reduce the
operation count further. Early adapters, such as the devel-
opers of TURBOMOLE [11], lead by Reinhart Ahlrichs,
developed a semi-direct code where expensive integrals
were stored on disk rather than recomputed.
In the integral-direct SCF scheme, it becomes attrac-
tive to develop more involved methods to accelerate con-
Figure . The occupation numbers of the natural orbitals (NO) of
vergence: a number of authors [1215] had shown the
the neon atom showing a regular pattern which permits a system- benefit of second-order methods using an exponential
atic truncation of the NO space: a successive expansion of a min- parametrisation of the orbital rotations between occupied
imal basis from [s p] to [s p d], [s p d f] and [s p d f and virtual space to converge the HartreeFock energy
g] includes all NOs within a given occupation number threshold calculation. In a 1992 article, Thomas Fischer and Jan
(quote from []).
Almlf presented a method that allows to recursively
update the inverse Hessian from gradient and displace-
ment information collected at each iteration, thus avoid-
At the latest, with the massive direct SCF calculations
ing the storage of the full matrix [16]. This same scheme
on the thermodynamic stability of C60 performed on
can also be used for geometry optimisation and be com-
the Minnesota Supercomputer Institute Cray-2 in 1986
bined with Pulays direct inversion of the iterative sub-
involving over 1000 contracted basis functions [10], the
space algorithm (DIIS [17,18] and GDIIS for geometry
integral-direct approach was readily accepted by the
optimisation [19]) for further acceleration.
community. One reason for the success of the integral-
In 1988, Martin Head-Gordon, John A. Pople and
direct approach was the fact that a few requirements that
Michael J. Frisch [20] argued that it is desirable to extend
are rather obvious were successfully addressed (a quote
the direct approach pioneered by Almlf and co-workers
from [5]):
to correlated methods presenting a CPU-bound scheme
r the integral evaluation must be as fast as possible; for the second-order Mller-Plesset (MP2) energy cal-
r the number of SCF iterations must be minimal; culation implemented in their GAUSSIAN88 program
r in any iteration, the amount of data to be recom- [21]. In fact, only a few months before, S. Sb and Jan
puted must be minimal. Almlf had presented their own approach [22], in which
the correlation energy can be built directly from atomic
The same requirements apply also in traditional cal- integrals. The early applications of the scheme, where the
culations but then carry considerably less weight. Given calculated integrals are transformed directly to the molec-
that the density matrix is known at each iteration, a better ular orbital (MO) basis without resorting to external
2036 H. P. LTHI AND T. HELGAKER

storage, showed that the CPU time for the MP2 calcula-
tion is dominated by the integral evaluation. The authors
concluded that if the resources allow a direct SCF calcu-
lation for a given system, then the second-order energy
can be obtained for an additional fraction of the cost.

2.3. From vector computing to the basis-set limit


With the advent of vector and shared-memory multi-
processor computers in the early 1980s, new challenges
and opportunities emerged. To take advantage of the new
architectures, algorithms had to be redesigned and codes
rewritten. Segmented orbital contraction, in which each
primitive basis function contributes to one contracted Figure . (Colour online) The graphical event log-le of the rst
function only, was at the time by far the most popular globally distributed locally parallel Hartree-Fock calculation
involving servers on both sides of the Atlantic returning GFLOPS
choice for one-electron basis sets but turned out to inhibit
Downloaded by [Chulalongkorn University] at 17:56 13 September 2017

performance. The availability of the servers (number of CPUs in


efficient vectorisation. Adapting his MOLECULE inte- parenthesis)is given in terms of per cent of processors. The eval-
gral code to vector processing in the mid 1980s, Almlf uation of the Fock matrix was split into batches. The transfer of
implemented general contraction, in which each prim- the partial results happened to be fairly synchronous. The transfer
itive orbital may contribute to several contracted func- times across the Atlantic are visibly larger. The processing of the
tions, as proposed by Raffenetti in 1973 [23]. General one-electron integrals and the diagonalisation are performed by
the client running on server .
contraction has a higher floating-point operation count
than does segmented contraction, but this additional cost
is offset by an efficient vectorisation of the transformation
2.4. Parallel and network computing for large SCF
from primitive to contracted orbitals. As it turned out,
calculations
this minor technical change in the MOLECULE integral
code in response to changes in computer architecture had The integral-driven HartreeFock method lends itself to
far-reaching consequences for how we design and per- parallelisation much more easily than the conventional
form quantum-chemical calculations. disk-based implementation. The most straightforward
In Fritz Schaefers words from 1971 [24], quoted by approach is to have each slave process a batch of inte-
Jan Almlf in 1988 [25], the selection of an appropriate grals and to build from these a private copy of the Fock
atomic-orbital basis is more art than science. Specifically, matrix. Subsequently, the master process collects the par-
in post-HartreeFock calculations, there was at the time tial Fock matrices from its slaves to determine the energy
no systematic way to improve a basis set, making it diffi- and the new density matrix, which then is broadcast to
cult to estimate the deviation from the basis-set limit. the slaves in case another SCF cycle has to be performed.
Exploiting general contraction, Almlf and Taylor With this simple scheme of parallelisation, DISCO was
introduced the atomic natural orbital (ANO) basis sets among the first application codes to reach Billion Floating
in 1987 [26], making the important observation that the Point Operations per second (GFLOPS) performances on
occupation numbers of the ANOs in atomic calculations an eight-processor Cray YMP computer [29].
(Figure 3) provide an excellent criterion for their inclu- Obviously, the slaves do not need to be running on
sion in molecular calculations of dynamical correlation. the same machine, but can be distributed over a net-
Their work provided the inspiration for Dunnings hugely work of multiprocessor computers at geographically dif-
successful correlation-consistent polarised basis sets in ferent locations connected via the Internet [30,31]. In
1989 [27] (in which basis-set inclusion is based on the September 1991, in a Hartree-Fock calculation using a
related energy criterion in atomic systems) and later to wide-area network with servers on both sides of the
the two-point basis-set extrapolation scheme of Helgaker Atlantic, GFLOPS performance during regular service
and co-workers in 1999 [28]. Exploiting the underly- hours was observed (see Figure 4 or [30] for more details).
ing principal (rather than partial-wave) expansion of the Later, speedups of close to 30 and a performance of 16.2
ANO and correlation-consistent basis sets, such extrapo- GFLOPS were recorded for a network of two (dedicated)
lation schemes reduce the error in the correlation energy 16-processor Cray C90 computers of the Cray Corporate
by an order of magnitude at little or no cost, thereby Network and the Pittsburgh Supercomputer Center (see
reaching chemical accuracy for the dynamical correlation Table 3 in [31]). The communication between master and
energy. slaves was through asynchronous remote procedure calls
MOLECULAR PHYSICS 2037
Downloaded by [Chulalongkorn University] at 17:56 13 September 2017

Figure . Per Siegbahn, Jan Almlf and Ulf Wahlgren at their hosts (Bjrn Roos (leftmost)) cottage in Smedjebacken near Lund around
.

2.5. Integral approximations and the Laplace


transform
So far, Jan Almlf s research had focused on accurate
first principles methods, strictly avoiding approaches that
would introduce uncontrollable or even unpredictable
errors. Inspired by the work of Christian van Alsenoy
[33], who thoroughly explored the multiplicative integral
Figure . Ferrocene, next to the porphyrins (see Figure ), accom- approximation, an approach suggested by Peter Pulay to
panied Jan Almlf over his entire career: from , HartreeFock accelerate two-electron integral calculation by expanding
calculations on the Mssbauer shift in ferrocene and ferricinium
products of Gaussians in auxiliary basis set, Almlf, Vah-
with Ulf I. Wahlgren and Paul S. Bagus [], via the rst direct SCF
calculation at the HartreeFock basis-set limit [], to giving the tras and Feyereisen showed that significant gains in com-
nal hint to the solution of the metal to ligand distance issue using puter time can be obtained, at no loss of accuracy, if a
a precursor of coupled cluster theory []. suitable expansion basis is chosen [34]. Similar ideas were
used by Dunlap in DFT [35,36], often referred to by Jan
via the Internet using a self-written package [32]. This all Almlf as Density Functional Technology (see e.g. Intro-
happened at a time well before grid computing became a duction in [34]). Such expansions of orbital products are
major topic in computing. today heavily used in all of quantum chemistry and were
Even though it received much attention by the com- essential for the MP2-R12 method as developed by Wim
munity of computational scientists, the limitations of net- Klopper, who was a post-doctoral fellow of Jan Almlf s
work computing soon became evident. Issues such as in the early 1990s [37].
fault-resistance, fault-tolerance or balancing the load on a The presence of the denominator in the con-
(heterogenous) network of computers running under dif- ventional expression for the MP2 energy, E (2) =
1 
ferent schedulers would require a substantial effort. More 4 i jab abi j2 /(a + b i j ) was an obsta-
importantly, there was the insight that the linear increase cle to the parallelisation of this method. In 1991
in compute power generated by adding more and more [38], Almlf showed that the Laplace transformation
1
computers to the network would not make much larger  the energy denominator (a + b i j ) =
of
systems accessible as long as the underlying computa- 0 exp[(a + b i j )t]dt allows the orbital
tional algorithms did not scale linearly with system size. energies to be transferred into the respective MOs,
2038 H. P. LTHI AND T. HELGAKER

leading to transformed orbitals i (t) = (0)exp (i t/2). methods introduced by Roos, Siegbahn and co-workers
The resulting
  Laplace-transformed 2 energy expression [44,45]. The most notable contribution of the Oslo group
E (2) = 0 i j,ab a(t )b(t )i(t ) j(t ) dt becomes embar- was to the NewtonRaphson formulation of the method
rassingly simple to parallelise. The numerical integration [46], allowing to reach convergence faster, also for excited
can be efficiently and robustly calculated using standard state calculations. The CASSCF method was applied to
numerical quadrature schemes. explore the full potential surfaces of small molecules with
Almlf pointed out that much of the significance of a large number of valence states within a comparatively
the above lies in the fact that a canonical representa- narrow energy range (such as BO), highly polar species
tion [of the molecular orbitals] is no longer needed, (such as LiB) [4753] or chemical reactions [54,55].
which leaves some additional flexibility in defining dif- In the 1990s, Jan Almlf s friendship with Odd
ferent types of orbital rotations for computational conve- Gropen (19412005) at the University of Troms(now
nience. Here, computational convenience implies orbital the Arctic University of Norway) brought him back
localisation to reduce the orbital space and cost of inte- to relativistic quantum chemistry, after initial work in
gral transformation. Together with Marco Hser [39] the field with Knut Fgri and Hans H. Grelland at
and PhD-student Angela K. Wilson [40], he showed that the University of Oslo in the early 1980s. With Odd
the quadrature error can be controlled and that differ- Gropen, he co-authored six publications on relativ-
Downloaded by [Chulalongkorn University] at 17:56 13 September 2017

ent localisation methods can be employed to increase the ity [5661]. Much of the focus of this research was
sparsity of the integral arrays, thus substantially reduc- the accurate evaluation of spinorbit coupling in PdH
ing the memory storage requirements. Today, the Laplace (needed for correct state ordering) using two- and four-
transform method is his most frequently cited work. component multi-reference configuration interaction
Computational performance and controllable trade- (CI) methods. Today, the annual AlmlfGropen lectures
offs between speed and accuracy are also the focus of one (http://www.ctcc.no/events/almlof-gropen-lecture) hon-
of Almlf s last scientific ventures: the separate calcula- our the memory of two central scientists in quantum-
tion of Coulomb and exchange contributions. Inspired chemical research in Norway.
by the quest for linear scaling in the DFT community,
the evaluation of the Coulomb and exchange matrices
was decoupled, thereby providing the freedom to pursue
2.7. Challenges from real chemistry
different specialised algorithms for the evaluation of each.
Together with his students Eric Schwegler and Matt Chal- Jan Almlf did not have a specific chemical agenda
lacombe, he developed a method for the fast construction rather, his interest in chemistry was focused on the under-
of the Coulomb matrix [41,42]. Using a combination of standing of electronic structure and molecular proper-
multipole expansion and explicit integral evaluation, the ties at large. Still, ferrocene (Figure 6) as well as por-
authors calculated the Coulomb contributions to the Fock phins and porphyrins (with or without transition-metal
matrix at sub-quadratic scaling for 560 membered water centres) received much attention throughout his entire
clusters and up to 16-membered polyglycine -helices. career indeed, it was a study of ferrocene that gave the
The follow-up article on the linearly scaling computa- impetus to the development of the direct SCF method.
tion of the HartreeFock exchange matrix, published in From a chemical perspective, being able to reach the one-
1996 [43], does not carry Jan Almlf s name; Eric Schwe- particle basis-set limit gave proof that the HartreeFock
gler and Matt Challacome dedicate the extension of this method fails to reproduce the molecular structure of fer-
research to his memory. rocene and other transition-metal compounds [62]. In
the case of ferrocene, the metalligand bond length at the
HartreeFock limit was 1.89 A, in poor agreement with
2.6. Method development and molecular property
the (unchallenged) experimental value of 1.65 A. In the
evaluation
case of iron pentacarbonyl (Fe(CO)5 ), the axial iron to
As a young professor in Oslo, next to his focus on carbon bond length is again much longer than the exper-
faster and larger calculations, Jan Almlf also had a imental value (2.05 vs. 1.81 A), whereas the equatorial
strong ambition towards more sophisticated methods. bond distance is only marginally longer (1.88 vs. 1.83 A)
Together with his colleagues Roos and Siegbahn (Figure [63].
5), his co-workers Anders Heiberg and Peter Ruoff, along The failure of the HartreeFock model to describe
with his frequent visitors Peter R. Taylor (NASA Ames) bonding in transition-metal compounds caused major
and Alexander Nemukhin (Moscow State University), irritation in the community. On the other hand, early
he further developed and applied multi-configuration DFT calculations did not encounter this problem to the
SCF, in particular CASSCF (complete active space SCF) same degree [6466] on the contrary, the success of DFT
MOLECULAR PHYSICS 2039

Table . The most frequently cited articles of Jan Almlfs. Even today, years after he passed away, his work is being cited more
than times a year.
Title Authors Source Year Ref. Cit.

Atomic Natural Orbitals and the Calculation of Atomic and Molecular Almlf, Taylor JCP []
Properties
Integral Approximations for LCAO-SCF Calculations Vahtras, Almlf, Feyereisen CPL []
General Methods for Geometry and Wave-Function Optimization Fischer, Almlf JCP []
The Complete Active Space SCF (CASSCF) Method in a Siegbahn, Almlf, Heiberg, Roos JCP []
Newton-Raphson Formulations with Application to the HNO Molecule
Principles for a Direct SCF Approach to LCAO-MO ab initio Calculations Almlf, Faegri, Korsell JCC []
Avoiding the Integral Storage Bottleneck in LCAO Calculations of Sb, Almlf CPL []
Electron Correlation
A Theoretical Study of Multidimensional Nuclear Tunneling in Shida, Barbara, Almlf JCP []
Malonaldehyde
Ab initio Studies on the Thermodynamic Stability of the Icosahedral Lthi, Almlf CPL []
C- Molecule Buckminsterfullerene
Elimination of Energy Denominators in Moller-Plesset Almlf CPL []
Perturbation-Theory by a Laplace Transform Approach
The Equilibrium Geometry of C as Predicted by nd-Order (MP) Hser, Almlf, Scuseria CPL []
Perturbation-Theory
Publications
Downloaded by [Chulalongkorn University] at 17:56 13 September 2017

Sum of the times cited


Average citations per item .
h-index

with transition-metal systems opened the doors to accep- of the machine, Almlf and co-workers came to the con-
tance of the method in chemistry. clusion that comparison of the energy per carbon atom
At the time, it was clear that electron correlation would computed for C54 and Buckminsterfullerene shows that
need to be addressed in calculations on transition-metal the soccerball shaped C60 molecule is indeed more sta-
compounds, but it would take years before the problem ble than the single-layer sheet of graphite [71]. Later, this
was finally solved. While early multiconfiguration self claim was confirmed by computations on much larger
consistent field (MCSCF) and 18-electron CI calculations sheets of graphite (with up to 150 carbon atoms) and by
on ferrocene clearly showed an improvement, the metal comparison to diamond-like structures (with up to 84
ligand distance was still 0.07 A longer than the experi- carbon atoms) [10].
mental reference. Correlating the entire valence space of The fact that Buckminsterfullerene may well be ther-
66 electron was at the time difficult and would call for modynamically stable was an encouraging message to its
size-consistent methods. Early MP2 calculations includ- discoverers (personal communication). Later, after the
ing the entire valence space resulted in too short metal new form of elemental carbon was isolated and charac-
ligand distances. In a 1991 article, Almlf and his stu- terised by Krtschmer, Huffmann and co-workers [72],
dent Changyok Park, using modified coupled-pair func- the calculations of the equilibrium geometry of C60 and
tional calculations with dispersion corrections derived derivatives reported by Almlf, Hser and Scuseria [73],
from accompanying MP2 calculations, correctly repro- and by Scuseria [74], marked some of the largest MP2
duced the molecular structure of ferrocene, highlight- calculations performed to that date (well beyond 1000
ing the importance of dispersion interactions [68]. In contracted basis functions). These calculations, involving
1996, a Coupled Cluster calculation with full treatment codes other than DISCO, showed the acceptance and the
of Single and Double excitations, plus perturbative cor- power of the integral-direct methods.
rection for Triple excitations [CCSD(T)] study of Koch, Trained as a crystallographer, hydrogen bonds and
Jrgensen and Helgaker agreed fully with experiment, hydrogen (proton) transfer were phenomena that fas-
demonstrating that ferrocene is not a multi-reference cinated Jan Almlf since the early days of his career. In
system [69]. the 1970s, he published nearly 20 papers that carry the
The controversy regarding the existence of Buckmin- term hydrogen in their title, some of which focus of por-
sterfullerene, proposed in 1985 by Richard Smalley and phyins or their building blocks. In the 1990s, with tools
co-workers [70], triggered Jan Almlf s interest. Based on much more advanced than the semi-empirical methods
preliminary HartreeFock calculations performed on the applied in the early days, an extensive collaboration with
MSI Cray-2 computer, using a version of the direct SCF colleagues of the University of Minnesota faculty, Paul G.
code that would keep part of the two-electron integrals in Gassman and Abhik Ghosh, on the electronic structure of
the 256 million double precision word central memory porphyrins and their response to peripheral substituents
2040 H. P. LTHI AND T. HELGAKER

[7584] evolved. A collaboration with Paul F. Barbara Notes


and post-doctoral student Norihiro Shida concerned
1. Usually referred to as the 19631974 generation of com-
proton tunnelling [8588]. Of particular interest was puters, such as the CDC Cyber 6000 series, the Univac
malonaldehyde, an experimentally well explored but 10/11 or the IBM 360/195.
challenging system to theory, known to yield a 21 cm1 2. Reference [2] is a translation of the original MOLECULE
tunnelling splitting due to the intramolecular keto-enol technical report [1] provided by Peter R. Taylor and pub-
tautomerism. Using a reaction surface Hamiltonian and lished in the Jan Almlf memorial issue of Theoretical
Chemistry Accounts [4].
a combination of ab intio SCF and Modified Coupled 3. these results were published only much later; see also ref-
Pair Functions (SCF-MCPF) calculations to first time erence 23 in [68]
construct a three-dimensional potential energy surface, 4. Which at the time was a huge memory, comparable to the
they obtained an effective tunnelling path that strongly total external storage available in an academic compute-
deviated from the minimal energy path. Even today, this centre, and often difficult to explain to colleagues who
thought that this cant possibly be true
work gets considerable attention (see also Table 1).
Other collaborations with University of Minnesota
faculty involved the work on degeneracy-corrected per- Acknowledgments
turbation theory for electronic structure calculations with
Downloaded by [Chulalongkorn University] at 17:56 13 September 2017

Don Truhlar [89]. Don Truhlar and Jan Almlf also were This article is dedicated to Elisabeth Almlf. First as graduate
students, then as post-docs and later as frequent visitors, we
an important and well-heard voice for supercomputing in
both enjoyed the great hospitality of the Almlf family.
chemistry [90,91].

Disclosure statement
3. Scientific legacy No potential conflict of interest was reported by the authors.

Among Jan Almlf s contributions to computational


References
quantum chemistry, three items stand out. Perhaps the
most visible are integral-direct schemes: they truly made [1] J. Almlf, Molecule (University of Stockholm Institute of
larger systems accessible, also for post-HartreeFock Physics Report 1972).
[2] J. Almlf, Theor. Chem. Accounts 97(14), 10 (1997).
methods. The ANO basis sets allowed basis-set error
[3] B.O. Roos, Lecture Notes in Quantum Chemistry: Euro-
in correlated calculations to be controlled and opened pean Summer School in Quantum Chemistry (Springer-
the door to extrapolation schemes. Finally, The Laplace- Verlag Berlin Heidelberg, 1992, Lecture Notes in Chem-
transform extended the efficiency and applicability of istry, Vol. 58).
MP2 theory and still finds new uses. The corresponding [4] O. Gropen, B.O. Roos, P.E.M. Siegbahn, P.R. Taylor, and
publications are among his most frequently referenced D.G. Truhlar, Jan Erik Almlf Memorial Issue, J. Mol.
Struct.: THEOCHEM 388, (1997).
and still frequently cited today; see his top-10 articles in [5] J. Almlf and P.R. Taylor, in Advanced Theories and
Table 1. Computational Approaches to the Electronic Structure of
Most of his research was on the development of meth- Molecules, edited by C.E. Dykstra (Springer Netherlands,
ods and algorithms that would perform well on the D. Reidel Publishing Company, 1984; 10.1007/978-94-
most advanced computer architectures. Often, he took up 009-6451-8), Chap. Computational Aspects of Direct and
MCSCF Methods, Nato Science Series C, pp. 107125,
existing methods, some of which had not gotten the atten-
10.1007/978-94-009-6451-8.
tion they deserved, and transformed them to deliver the [6] J. Almlf, Int. J. Quantum Chem. 8(6), 915 (1974).
best possible performance. He used to say that he would [7] H. Lthi, J. Ammeter, J. Almlf, and K. Korsell, Chem.
rather be running the most recent code on older hard- Phys. Lett. 69(3), 540 (1980).
ware, than running older code on the most recent hard- [8] J. Almlf, J. Faegri, and K. Korsell, J. Comput. Chem. 3(3),
ware. Given his record and his influence on method and 385 (1982).
[9] H. Lthi, J. Ammeter, J. Almlf, and K. Faegri, J. Chem.
code development, Jan Almlf stands out as one of the Phys. 77(4), 2002 (1982).
pioneers of computational quantum chemistry. [10] J. Almlf and H. Lthi, in Supercomputer Research in
At the same time, Almlf was among the scientists Chemistry and Chemical Engineering, edited by K.F.
who helped turn computational chemistry into a well- Jensen D.G. Truhlar (American Chemical Society, 1987),
accepted tool in chemical research. His work on hydrogen Chap. Theoretical Methods and Results for Electronic
Structure Calculations on Very Large Systems, ACS Sym-
bonding, on the transition-metalligand interactions and
posium Series, pp. 3548.
on the molecular and electronic structure of allotropic [11] R. Ahlrichs, M. Br, M. Hser, H. Horn, and C. Klmel,
carbon compounds carried a strong message and served Chem. Phys. Lett. 162(3), 165169 (1989).
as inspiration and motivation for many other chemists. [12] D. Thouless, Nuclear Phys. 21, 225 (1960).
MOLECULAR PHYSICS 2041

[13] J. Douday, Y. Ellinger, R. Subra, and B. Levy, J. Chem. [47] A.V. Nemukhin, J. Almlf, and A. Heiberg, Chem. Phys.
Phys. 72, 1452 (1980). 57(12), 197 (1981).
[14] G. Bacskay, Chem. Phys. 61, 385 (1981). [48] J. Almlf, A.V. Nemukhin, and A. Heiberg, Int. J. Quan-
[15] M. Head-Gordon and J.A. Pople, J. Phys. Chem. 92, 3063 tum Chem. 20(3), 655 (1981).
(1988). [49] A.V. Nemukhin, J. Almlf, and A. Heiberg, Theor. Chim.
[16] T. Fischer and J. Almlf, J. Phys. Chem. 96(24), 9768 Acta 59(1), 9 (1981).
(1992). [50] H. Sellers, J. Boggs, A.V. Nemukhin, and J. Almlf, J. Mol.
[17] P. Pulay, Chem. Phys. Lett. 73(2), 393398 (1980). Struct.: THEOCHEM 85(12), 195 (1981).
DOI:10.1016/0009-2614(80)80396-4. [51] A.V. Nemukhin, J. Almlf, and A. Heiberg, Chem. Phys.
[18] P. Pulay, J. Comput. Chem. 3(4), 556560 (1982). Lett. 76(3), 601 (1980).
DOI:10.1002/jcc.540030413. [52] A.V. Nemukhin and J. Almlf, J. Mol. Struct.:
[19] P. Csszr and P. Pulay, J. Mol. Struct. 31, 114 (1984). THEOCHEM 253(C), 101 (1992).
[20] M. Head-Gordon, J.A. Pople, and M.J Frisch, Chem. [53] A. Heiberg, J. Almlf, and A.V. Nemukhin, Chem. Phys.
Phys. Lett. 153(6), 503 (1988). Lett. 88(4), 399 (1982).
[21] M.J Frisch, M. Head-Gordon, H.B. Schlegel, K. [54] P. Ruoff, S. Sb, and J. Almlf, Chem. Phys. Lett. 83(3),
Raghavachari, J. Binkley, C. Gonzalez, D. Defrees, 549 (1981).
D. Fox, R. Whiteside, R. Seeger, C. Melius, J. Baker, L. [55] P. Ruoff, J. Almlf, and S. Sb, Chem. Phys. Lett. 72(3),
Kahn, J. Stewart, E. Fluder, S. Tipiol, and J.A. Pople, 489 (1980).
GAUSSIAN88 (Gaussian Inc., Pittsburg, PA, 1988). [56] O. Gropen and J. Almlf, Chem. Phys. Lett. 191(34), 306
Downloaded by [Chulalongkorn University] at 17:56 13 September 2017

[22] S. Sb and J. Almlf, Chem. Phys. Lett. 154(1), 83 (1992).


(1989). [57] O. Gropen, J. Almlf, and U. Wahlgren, J. Chem. Phys.
[23] R. Raffenetti, J. Chem. Phys. 58(10), 4452 (1973). 96(11), 8363 (1992).
[24] S. Rothenberg and H.F. Schaefer III, J. Chem. Phys. 54(6), [58] M. Sjvoll, H. Fagerli, O. Gropen, J. Almlf, T. Saue, J.
2764 (1971). Olsen, and T.U. Helgaker, J. Chem. Phys. 107(14), 5496
[25] J. Almlf, T.U. Helgaker, and P.R. Taylor, J. Phys. Chem. (1997).
92(11), 3029 (1988). [59] J. Almlf and O. Gropen, Rev. Comput. Chem. 8, 203
[26] J. Almlf and P.R. Taylor, J. Chem. Phys. 92(1), 551 (1996).
(1990). [60] M. Sjvoll, H. Fagerli, O. Gropen, J. Almlf, B. Schim-
[27] T.H. Dunning Jr, J. Chem. Phys. 90, 1007 (1989). melpfennig, and U. Wahlgren, Theor. Chem. Accounts
[28] A. Halkier, T.U. Helgaker, P. Jorgensen, W. Klopper, and 99(1), 1 (1998).
J. Olsen, Chem. Phys. Lett. 302(56), 437 (1999). [61] M. Sjvoll, H. Fagerli, O. Gropen, J. Almlf, J. Olsen, and
[29] H. Lthi, J. Mertz, M.W. Feyereisen, and J. Almlf, J. T.U. Helgaker, Int. J. Quantum Chem. 68(1), 53 (1998).
Comput. Chem. 13(2), 160 (1992). [62] J. Almlf, K. Faegri, B. Schilling, and H. Lthi, Chem.
[30] H. Lthi and J. Almlf, Theor. Chim. Acta 84(45), 443 Phys. Lett. 106(4), 266 (1984).
(1993). [63] H. Lthi, P.E.M. Siegbahn, and J. Almlf, J. Phys. Chem.
[31] H. Lthi, Theor. Chem. Accounts 97(14), 211 (1997). 89(11), 2156 (1985).
[32] P. Arbenz, C. Sprenger, H. Lthi, and S. Vogel, Concur- [64] C. Sosa, J. Andzelm, B.C. Elkin, E. Wimmer, K.D. Dobbs,
rency, Pract. Exp. 7(2), 121 (1995). and D.A. Dixon, J. Phys. Chem. 96(16), 6630 (1992).
[33] C. Van Alsenoy, J. Comput. Chem. 9(6), 620 (1988). [65] L. Fan and T. Ziegler, J. Chem. Phys. 95(10), 7401
[34] O. Vahtras, J. Almlf, and M.W. Feyereisen, Chem. Phys. (1991).
Lett. 213(56), 514 (1993). [66] B. Delley, M. Wrinn, and H. Lthi, J. Chem. Phys. 100(8),
[35] D.I. Dunlap, J. Chem. Phys. 78, 3140 (1983). 5785 (1994).
[36] D.I. Dunlap and N. Rosch, J. Chim. Phys. Phys.-Chim. [67] P.S. Bagus, U. Walgren, and J. Almlf, J. Chem. Phys.
Biol. 86(4), 671 (1989). 64(6), 2324 (1976).
[37] W. Klopper and J. Almlf, J. Chem. Phys. 99(7), 5167 [68] C. Park and J. Almlf, J. Chem. Phys. 95(3), 1829 (1991).
(1993). [69] H. Koch, P. Jorgensen, and T.U. Helgaker, J. Chem. Phys.
[38] J. Almlf, Chem. Phys. Lett. 181(4), 319 (1991). 104(23), 9528 (1996). DOI: 10.1063/1.471695.
[39] M. Hser and J. Almlf, J. Chem. Phys. 96(1), 489 (1992). [70] H.W. Kroto, J.R. Heath, S.C. OBrian, R.F. Curl, and R.E.
[40] A.K. Wilson and J. Almlf, Theor. Chem. Accounts 95(1 Smalley, Nature 318(6042), 162 (1985).
2), 49 (1997). [71] H. Lthi and J. Almlf, Chem. Phys. Lett. 135(45), 357
[41] M. Challacombe, E. Schwegler, and J. Almlf, Chem. (1987).
Phys. Lett. 241(12), 67 (1995). [72] W. Krtschmer, L. Lamb, K. Fostiropoulos, and D. Huff-
[42] M. Challacombe, E. Schwegler, and J. Almlf, J. Chem. man, Nature 347(6291), 354 (1990).
Phys. 104(12), 4685 (1996). [73] M. Hser, J. Almlf, and G.E. Scuseria, Chem. Phys. Lett.
[43] E. Schwegler and M. Challacombe, J. Chem. Phys. 105(7), 181(6), 497 (1991).
2726 (1996). [74] G.E. Scuseria, Chem. Phys. Lett. 176(5), 423 (1991).
[44] B.O. Roos, P.R. Taylor, and P.E.M. Siegbahn, Chem. Phys. [75] A. Sargent, M. Rollog, J. Almlf, P.G. Gassman, and J.
48(2), 157 (1980). Gerlt, J. Mol. Struct.: THEOCHEM 388(13), 145 (1996).
[45] P.E.M. Siegbahn, A. Heiberg, B.O. Roos, and B. Levey, [76] A. Ghosh, J. Fitzgerald, P.G. Gassman, and J. Almlf,
Phys. Scr. 21(34), 323 (1980). Inorg. Chem. 33(26), 6057 (1994).
[46] P.E.M. Siegbahn, J. Almlf, A. Heiberg, and B.O. Roos, J. [77] A. Ghosh, P.G. Gassman, and J. Almlf, J. Am. Chem. Soc.
Chem. Phys. 74(4), 2384 (1981). 116(5), 1932 (1994).
2042 H. P. LTHI AND T. HELGAKER

[78] J. Almlf, T. Fischer, P.G. Gassman, A. Ghosh, and M. [85] N. Shida, J. Almlf, and P.F. Barbara, J. Phys. Chem.
Hser, J. Phys. Chem. 97(42), 10964 (1993). 95(25), 10457 (1991).
[79] P.G. Gassman, A. Ghosh, and J. Almlf, J. Am. Chem. Soc. [86] N. Shida, P.F. Barbara, and J. Almlf, J. Chem. Phys. 94(5),
114(25), 9990 (1992). 3633 (1991).
[80] A. Ghosh, J. Almlf, and P.G. Gassman, Chem. Phys. Lett. [87] N. Shida, P.F. Barbara, and J. Almlf, J. Chem. Phys. 91(7),
186(1), 113 (1991). 4061 (1989).
[81] A. Ghosh, J. Almlf, and L. Que Jr, Angew. Chem. [88] N. Shida, J. Almlf, and P.F. Barbara, Theor. Chim. Acta
(International Edition in English) 35(7), 770 76(1), 7 (1989).
(1996). [89] X. Assfeld, J. Almlf, and D.G. Truhlar, Chem. Phys. Lett.
[82] A. Ghosh and J. Almlf, J. Phys. Chem. 99(4), 1073 241(4), 438 (1995).
(1995). [90] J. Almlf and D.G. Truhlar, Interdiscip. Sci. Rev. 15(3),
[83] A. Ghosh, J. Almlf, and L. Que Jr, J. Phys. Chem. 98(21), 252 (1990).
5576 (1994). [91] J. Almlf, D.G. Truhlar, H. Davis, K. Jensen, M. Tirrell,
[84] A. Ghosh and J. Almlf, Chem. Phys. Lett. 213(56), 519 and T. Lybrand, Int. J. High Perform. Comput. Appl. 2(2),
(1993). 5 (1988).
Downloaded by [Chulalongkorn University] at 17:56 13 September 2017