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CONTINUUM SOLVATION MODELS IN

GAUSSIAN 03

Dr. Ivan Rostov


Australian National University,
Canberra

E-mail: Ivan.Rostov@anu.edu.au
OUTLINE

 Types of solvent effects and solvent models


 Overview of solvation continuum models
available in Gaussian 03.
 Summary of Gaussian keywords

 Applications

 Recommendations

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SOLVENT EFFECTS
Nicolai Alexandrovich Menshutkin, Z. Physik. Chem. 1890, 5, 589

NH3 CH3Cl NH3CH3+ Cl-

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SOLVENT EFFECTS

 The solvent environment influences all of


these:
 Structure
 Energies
 Reactionand activation energies
 Bond energies

 Spectra
 Rotational (Microwave)
 Vibrational (IR, Raman)
 Electronic (UV, visible)

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METHODS FOR TREATMENT OF
SOLVATION
 Supermolecule
 Solute and some number of solvent molecules are included in one
large QM calculation
 Molecular Mechanics Force Fields
 Simple classical force fields allows us to include a large number of
solvent molecules
 Continuum models
 Explicit consideration of solvent molecules is neglected
 Solvent effects are described in terms of macroscopic properties of
the chosen solvent (e, <Rsolvent>)
 Hybrid/mixed:
 Supermolecule + Continuum model
 QM + MM
 QM + MM + Continuum model
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SOLVATION PROCESS
 disp.-rep.  disp.-rep.  elec
FiN FiN  FiN

1) Creation of cavity 2) Turning on 3) Turning on


dispersion and electrostatic forces
repulsion forces

U solv  U cav  U disp.- rep.  U elec.

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BASICS OF THE CONTINUUM MODEL
THEORY
 Solvent is described in terms of macroscopic
properties
 Solvent is dielectric medium (uniform, normally),
characterized by the dielectric constant e0
 Polarization of solvent is expressed in terms of the
surface charge density on the cavity surface
 Polarization produces the electric field in the cavity
making an effect on solute
 Dispersion-Repulsion and Cavitation are added
separately, or ignored

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THE ELECTROSTATIC PROBLEM
Poisson equations
- 4 r  Vi 
 2  
 0 r  Ve 
with boundary conditions
on S:
in  out
in 
e= 1  e out
S n n
e= e0

Solution is calculated as
 (r)  (r)
 (r)   d r
3
  d r
2

V
r - r S
r - r
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BORN MODEL
 A single charge inside a spherical cavity
 No constructing of the cavity surface elements, because
the Poisson equation is solved analytically

 1  Q2
U solv  -1 - 
 e0  R

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ONSAGER MODEL
 Spherical cavity μ2 e 0 -1
E  H- 3 
 Dipolar reaction field R 2e 0  1
 No constructing of the cavity surface elements, because
the Poisson equation is solved analytically
 Keywords in Gaussian:
SCRF(Dipole,A0=value,Dielectric=value)
 Area of applicability:
 Solute shape is close to spherical
 Solute is polar (m >> 0)
 References
 L. Onsager, J. Am. Chem. Soc. 58, 1486 (1936).
 M. Wong, M. Frisch, K. Wiberg, J. Am. Chem. Soc. 113, 4476
(1991).
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POLARIZED CONTINUUM MODEL (PCM)
 Realistic molecular shape of the cavity (interlocking spheres
around each atom or group, or isodensity surface)
 Induced surface charges represent solvent polarization
 Includes free energy contributions from forming the cavity
and dispersion-repulsion
 Comes in number of “flavours”:
IEFPCM, CPCM, DPCM, IPCM, or SCIPCM
 Keywords in Gaussian:
 SCRF(Solvent=, PCM specific options)
 References:
 E. Canses, B. Mennucci, J. Tomasi, J. Chem Phys. 107, 3032 (1997).
 J. Tomasi, M. Persico, Chem. Rev. 94,2027 (1994).
 J. Tomasi, B. Mennucci, R. Camm, Chem. Rev. 105, 2999 (2005).

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PCM, THE CAVITY CONSTRUCTION
 Interlocking spheres around atomic groups
 This is default in Gaussian 03
 A choice of united atoms radii set, RADII=UAO (default), UAHF, UAKS,
or UFF
 Interlocking spheres around each atom
 Radii=Pauling (or Bondi)
 Requires the scaling factor ALPHA by which the sphere radius is
multiplied. The default value is 1.0 though should be 1.2
 A number of keywords is provided to add extraspheres when
necessary
 A number of keyword is provided to govern the size and
number of surface elements (tesserae)

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PCM, THE CAVITY VIEW
 Keyword: GeomView
 Creates files in GeomView format to visualize the cavity
construction and the charge distribution on the cavity:
 tesserae.off
 charge.off
Files are readable by GeomView, JavaView and other visualization software.

(C5NH12+)

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PCM, METHODS OF SOLVING OF THE SCRF
PROBLEM TO CALCULATE SURFACE CHARGES
 3   
 r    r    d r  r   2 r 
1 1 1
 d r    
2
 Iterative
V f0 n (r ) r - r  S
n (r ) r - r  
 Keyword: ITERATIVE
q
 Solves the PCM electrostatic problem  r   i
through a linear scaling iterative Si
method using a Jacobi-like scheme
 Advantageous when memory is
limited.
 Inversion
Keyword: INVERSION
 

 r  ˆ -1 (r, r ' )Vˆ (r, r' )  (r )
D
 Solve the PCM electrostatic problem to
calculate polarization charges through
the inversion matrix D with dimension
of NtesxNtes
 Gaussian 03 uses Inversion by default.

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DIELECTRIC PCM
 The original version of PCM
 Electrostatics directly from the cavity model
 Charges produces by discontinuity in the electric field
across the boundary created by the cavity
 Very sensitive to solute charge outside the cavity
 Only single point calculations
 No longer recommended

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INTEGRAL EQUATION FORMALISM PCM
(IEFPCM)
 Default in Gaussian 03
 Less sensitive to diffuse solute charge
distributions
 PCM + careful outlying charge corrections =>
IEFPCM

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CPCM (COSMO)
 Uses the assumption that the cavity surface to be
conductor-like
 This assumption simplifies the solution of Poisson
equation and calculation of the surface charges
 Results can be outputted in COSMO RS format
 Not recommended for solvents with low polarity
 It is more efficient in iterative regime

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ISODENSITY PCM (IPCM) AND
SELF-CONSISTENT ISODENSITY PCM (SCIPCM)
 Cavity formed using gas-phase static electronic isodensity
surface (IPCM)
 Less arbitrary than spheres on atoms
 Cavity changes with electron density and environment
 The default density value is 0.0004
 only single point calculations
 Self-Consistent Isodensity (SCIPCM)
 iterations are folded in SCF
 issues regarding scaling of charges still remain
 References
 J. Foresman, T.Keith, K. Wiberg, J. Snoonian, M. Frisch,
J. Phys. Chem. 100,16098 (1996).

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GAUSSIAN 03 KEYWORD EXAMPLES
SCRF(Dipole,A0=5.5,eps=78.39)

SCRF(IEFPCM) is the same as SCRF(PCM), or just SCRF

SCRF(CPCM,Solvent=THF,Read)

SCRF(IPCM)

SCRF(SCIPCM)

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SAMPLE INPUT FOR PCM CALCULATIONS
PCM solvation is
%chk=pip-pcm
#P HF/6-31g(d) SCRF(PCM,Solvent=Water,Read) test
requested. Solvent is
Water. Additional PCM
Piperidinium cation specific keywords are
provided
1 1
N
C 1 1.50977268
C 2 1.52365511 1 109.63925419
C 3 1.53136665 2 111.56508108 1 -55.04631728
C 1 1.50978576 2 113.42079276 3 57.07092348
C 4 1.53134037 3 110.99585756 2 54.90811126
H 1 1.00969298 5 109.64667654 6 -179.99768911
H 1 1.01028619 5 109.06107319 6 64.67690355
H 2 1.08151743 1 106.09798567 5 -64.03241054
H 2 1.08069845 1 107.09512052 5 179.68520816
H 3 1.08732966 2 109.45874935 1 67.33780856
H 3 1.08342937 2 107.81444282 1 -177.04873713
H 4 1.08661607 3 109.70973952 2 -66.50424273
H 4 1.08269752 3 109.4557835 2 176.38517116
H 5 1.08069728 1 107.09836585 2 -179.68240007
H 5 1.08151732 1 106.09918524 2 64.03563496
H 6 1.08732304 4 110.31444998 3 66.98445589
H 6 1.08344075 4 110.90163383 3 -175.10999479

PCMDOC
ITERATIVE PCM specific keywords
GEOMVIEW 20
SAMPLE OUTPUT

SCF Done: E(RHF) = -250.669391936 A.U. after 6 cycles


Convg = 0.7269D-05 -V/T = 2.0012
S**2 = 0.0000
--------------------------------------------------------------
Variational PCM results
=======================
<psi(f)| H |psi(f)> (a.u.) = -250.570493
<psi(f)|H+V(f)/2|psi(f)> (a.u.) = -250.669392
Total free energy in solution:
with all non electrostatic terms (a.u.) = -250.662541
--------------------------------------------------------------
(Polarized solute)-Solvent (kcal/mol) = -62.06
--------------------------------------------------------------
Cavitation energy (kcal/mol) = 16.10
Dispersion energy (kcal/mol) = -12.61
Repulsion energy (kcal/mol) = 0.81
Total non electrostatic (kcal/mol) = 4.30
--------------------------------------------------------------

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APPLICATIONS

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+
PIPEREDIN CATION (C5NH12 ),
FREE ENERGY OF HYDRATION
QM: HF/6-31G(d)
Method Gsolv, kcal/mol

SP SCRF(Dipole,A0=5.5) -30.6
SP SCRF(PCM) -56.0
SP SCRF(CPCM) -56.1
SP SCRF(IPCM) -59.4
SP SCRF(SCIPCM) -60.9

Opt SCRF(PCM) -56.3


Opt SCRF(CPCM) -56.4
PCM cavity was Opt SCRF(SCIPCM) -61.1
constructed of
1006 tesserae Experiment -60.0
Dipole, IPCM and SCIPCM results includes electrostatic effects only, sum of
non-electrostatic is + 4.3 kcal/mol (PCM). 23
ET SYSTEM
Donor = 4-Biphenyl
Acceptor = 2-Naphthyl
e-

D-SA → DSA-

Spacer: 5-a-androstane

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- -
ET system D SA → DSA

ET SYSTEM
D: 4-Biphenyl
A: 2-Naphthyl
S:5-a-androstane
87 atoms in total,
5158 tesserae created

ROHF/6-31G(d,p) SP SCRF(IEFPCM, Solvent=THF)

Method to solve Memory,M CPUs Time,


surface charges b min.
240 1 92.5
640 1 32
Matrix inversion
800 1 31
(default)
1600 1 30
1600 4 22
64 1 28
640 1 29
Iterative 800 1 27
1600 1 29
400 4 17.5 25
ET SYSTEM -
D SA → DSA
-

D: 4-Biphenyl
A: 2-Naphthyl
S:5-a-androstane
87 atoms in total,
5158 tesserae created

ROHF/6-31G(d,p) SP SCRF(СPCM, Solvent=THF)

Method to solve Memory,M CPUs Time,


surface charges b min.
240 1 29
640 1 29
Matrix inversion
800 1 28
(default)
1600 1 28
1600 4 19
64 1 16
640 1 16
Iterative 800 1 16
1600 1 16
800 4 5.75 26
ET SYSTEM
• In vacuo ROHF and UHF calculations fails to produce
the precursor state. Altering of MOs does not help.
• Polarization field of solvent makes it possible to
obtain solution (with solvent polarization effects
included!) for both precursor and successor states using guess=alter option
and altering order of HOMO
• G = -7.7 kcal/mol (IEFPCM)
and LUMO
• G = -9.6 kcal/mol (СPCM)
• G = -2.7 kcal/mol (СPCM, optimization, 78 hrs.)
• G = -5±1 kcal/mol (Experiment)

Blue structure is the precursor, 4-biphenyl is planar


Red structure is successor, 4-biphenyl dihedral angle is 42.9º 27
MENSHUTKIN REACTION

NH3 CH3Cl NH3CH3+ Cl-

 What is G and G≠ for the reaction?


 What is the nature of the transition state?
 How does solvent change the result?

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MENSHUTKIN REACTION

NH3 CH3Cl NH3CH3+ Cl-

Model G≠ G
Gas 43.7 120.0
Onsager 18.2 10.0
DPCM@Onsager 24.2 -21.0
CPCM 24.8 -21.5
Experiment – for CH3I
Gas ? 110
Solution 24 -30
Energies in kcal/mol
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MENSHUTKIN REACTION: TRANSITION STATE

Model C-N C-Cl H-N-C Cl-C-H

Gas 1.765 2.571 110.6 78.7

Onsager 2.273 2.250 112.6 94.2

CPCM 2.145 2.249 110.3 92.6

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RECOMMENDATIONS

 Preliminary in vacuo calculations (geometry and wavefunction


guess)
 In many cases SP SCRF after Optimization in vacuo is enough
 IEFPCM ( It is the default method in G03)
 When memory is limited, or the system is large, the Iterative
algorithm is faster and less demanding than Inversion
 When time is crucial, CPCM is recommended under some
conditions:
 polar solvent;
 keyword Iterative!

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