Computational and Experimental

Studies on the IR Spectra and

Structure of the Simplest Nitriles (C1
and C2), Their Anions, and Radicals
MIGLENA K. GEORGIEVA, EVELINA A. VELCHEVA
Department of Structural Organic Analysis, Institute of Organic Chemistry, Bulgarian Academy of
Sciences, Acad. G. Bonchev Str., Bl. 9, 1113 Sofia, Bulgaria

Received 28 October 2004; accepted 15 February 2005

Published online 5 December 2005 in Wiley InterScience (www.interscience.wiley.com).
DOI 10.1002/qua.20887

ABSTRACT: The structure and infrared spectra of formonitrile (hydrogen cyanide)

and acetonitrile, their anions, and radicals (45 species in all) have been studied by
density functional theory (DFT) B3LYP 6-31⫹⫹G(d,p) calculations. The results obtained
have been compared with the literature and original experimental data. The zero-point
vibrational energy (ZPVE)-corrected deprotonation energies of the studied (and other)
nitriles correlate fairly well (R ⫽ 0.94) with their pKa values, measured in dimethyl
sulfoxide (DMSO). The theoretical cyano stretching frequencies ␯C'N of the species
studied have been found to correlate satisfactorily (R ⫽ 0.97) with the experimental
ones. The latter correlation can be used for a theoretical estimation of ␯C'N of many
nitriles, their anions, and radicals. The geometry parameters for the molecules,
calculated by the same theoretical method, practically coincide with those determined
experimentally in the gas state. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem 106:
1316 –1322, 2006

Key words: IR; DFT; nitriles; anions; radicals; structure

radicals [1–17] (and references therein). The num-

Introduction ber of the quantum chemical investigations of these
species is still larger (e.g., Refs. [4, 16, 18 –32]). Un-

W e found in the literature numerous experi-

mental spectroscopic studies on hydrogen
cyanide, acetonitrile, and many of their anions and
Correspondence to: M. K. Georgieva; e-mail: miggeo@orgchm.
bas.bg
Contract grant sponsor: Bulgarian Council Research.
Contract grant number: 1213.
fortunately, direct comparison between theoretical
and experimental values would be neither produc-
tive nor informative, as the theoretical data were
obtained using a large variety of quantum chemical
methods: semi-empirical, ab initio, and density
functional. In several recent comparative studies,
we obtained the best spectral and structural predic-
tions within density functional theory (DFT) [33–

International Journal of Quantum Chemistry, Vol 106, 1316 –1322 (2006)

© 2005 Wiley Periodicals, Inc.
 STUDIES ON IR SPECTRA AND STRUCTURE OF NITRILES, THEIR ANIONS, AND RADICALS
38]. So, we shall try to show in the present work
that both the structure and the infrared (IR) spectra
of the title species can be described (and may be
predicted) satisfactorily by the DFT B3LYP
6-31⫹⫹G(d,p) method.
Experimental
The IR spectra were measured on a Bruker IFS
113v FTIR spectrometer in a CaF2 cell of 0.26 mm
path length [for the dimethyl sulfoxide (DMSO)
solutions] and in a CaF2 cell of 0.02 mm path length
for the water solutions, at a resolution of 1 cm⫺1
and 50 scans. KCN (Fluka, ⬎99.5%) and KC15N
(Berlin Chemie, 97.3% at. enrichment) were used in
the IR experiments.
Computations
Gaussian 98 software [39] was used for the
B3LYP 6-31⫹⫹G(d,p) calculations. According to the
program instructions, multiplicities 1 and 3 were
assumed preliminarily for singlets and triplets, re-
spectively. All computations were carried out on a
Pentium 2 PC. No scaling in the DFT force con-
stants was done. A standard least-squares program
was used for calculating the single-parameter linear
regression indices.
Results and Discussion
ENERGY ANALYSIS
The zero-point vibrational energy (ZPVE)-cor-
rected total energies of the molecules, anions, and
radicals studied are listed in Table I. The following
comments can be made on the corresponding data:
1. Hydrogen isocyanide HNC (singlet) 2a is
57.11 kJ mol⫺1 less stable than its isomer HCN
1a. This result is in qualitative agreement with
the instability of 2a, which was unknown until
the middle of the twentieth century. The hy-
pothetical hydrogen isocyanide (triplet) 3
⫹ ⫺
HON 'C O
¢¡ HON'C:
2a
HONAĊ
7 HOṄOĊ:
3 nitrile 6a (cf. above).
VOL. 106, NO. 6 DOI 10.1002/qua INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY 1317
should be much more unstable, by 488.25 kJ
mol⫺1, than 2a (unlike, e.g., cyanoisocyanide
NCNC, assumed [40] to be a triplet). The
above statement can be proved by the exper-
imental ␯CN (2009 cm⫺1) of HNC, which is not
away from ␯CN (near 2150 cm⫺1 [41]; see also
14a in Table I) of alkyl isocyanides, and by 888
cm⫺1 higher than that calculated for 3. In fact,
the latter value of 1124 cm⫺1 (Table I) corre-
sponds to ␯CON (1020 –1220 cm⫺1 [42]) of un-
conjugated CON groups (cf. the canonical
forms of 3 above).
2. By analogy, methylisocyanide CH3NC is by
88.80 kJ mol⫺1 lass stable than its isomer ace-
tonitrile CH3CN (cf. 6a, 14a).
3. On the other hand, Table I shows an example
where (unlike the HNC case) the hypothetical
singlet form 11a is 111.27 kJ mol⫺1 less stable
than the triplet one 12a. This result is in agree-
ment with the calculations of Maier et al. [16]
and with ␯CN (more precisely ␯CCN) mea-
sured, which corresponds to 12a– d, rather
than 11a– d (cf. Table I and the canonical
forms below):
⫹ ⫺
HOC̈OC'N ¢
O ¡ HOCACAN
11a
•
HOĊខ OC'N O
¢¡ HOCACAṄ
12a
4. Deprotonation of both HCN 1a and HNC 2a
results in the formation of a single anion, cy-
anide 4a. The gas-phase deprotonation ener-
gies ED ⫽ E(anion) ⫺ E(molecule) of a 1a and 2a
are 1457.43 and 1400.32 kJ mol⫺1, respectively.
So, if hydrogen isocyanide 2a were suffi-
ciently stable (but it is not), it would formally
be an essentially stronger Broensted acid, than
hydrogen cyanide 1a.
5. The ED value of acetonitrile 6a, 1546.33 kJ
mol⫺1 is much higher than the above (6a is a
very weak COH acid), and ED of its carbanion
is much higher, 2148.66 kJ mol⫺1. Neverthe-
less, Gornowicz and West [2] succeeded in
measuring the IR spectrum of the acetonitrile
dilitium derivative (8 in Table I).
6. According to the calculations, methylisocya-
nide (ED ⫽ 1591.45 kJ mol⫺1; cf. 14, 15) should
be a weaker COH acid than its isomer aceto-
TABLE I ______________________________________________________________________________________________
ZPVE-corrected total energies (hartree), theoretical and experimental (mainly literature) IR frequencies (cmⴚ1),
and integrated intensities (km molⴚ1) for the species studied.

B3LYP 6-31⫹⫹G(d,p) Experimental

Species Ecorr ␯CN ACN ␯CN ACN

1a HCN ⫺93.415841 2222 1.86 2129a 0.1e

2128b
2127c
2130d
1b DCN ⫺93.418292 2030 8.52 2046f
1c H13CN ⫺93.415983 2186 1.54
1d HC15N ⫺93.415926 2187 1.73
2a HNC (singlet) ⫺93.394082 2009 71.42 2029g
2b DNC (singlet) ⫺93.396625 1896 26.47 1940g
2c HN13C (singlet) ⫺93.394181 1967 69.04 1987g
2d H15NC (singlet) ⫺93.394174 1984 71.44 2004g
3 HNC (triplet) ⫺93.208070 1121 46.81
4a CN⫺ ⫺92.860589 2124 22.36 2054h
2079i 6.1i
4b 13
CN⫺ ⫺92.860691 2080 23.72
4c C N⫺15
⫺92.860666 2092 19.80 2046 i
6.6i
5a CN• ⫺92.712090 2151 15.48 2046g
5b 13
CN• ⫺92.712197 2106 14.84 2003g
5c C15N• ⫺92.712169 2118 15.01 2015g
6a CH3CN ⫺132.718787 2364 11.22 2267j 1.2j
2.0k
2249l 4.9l
2252m
6b CD3CN ⫺132.728622 2364 2.17 2257l 6.6l
2261m
6c CH313CN ⫺132.718994 2308 10.91
6d CH3C15N ⫺132.718892 2334 10.78 2222l 4.9l
⫺
7a CH2CN ⫺132.129667 2139 682.31 2051l 260l
2048n
2050m
⫺
7b CD2CN ⫺132.135164 2133 667.38 2051l
2043m
⫺
7c CH2 CN 13
⫺132.129874 2085 651.47
⫺
7d CH2C15N ⫺132.129767 2115 669.64 2029l
8 2⫺
CHCN ⫺131.311070 1882 1702.10 1820o
9 3⫺
CCN ⫺130.334209 1728 1091.75
10
CH2CN ⫺132.072646 2134 1.52
11a CHCN (singlet) ⫺131.370132 1928 11.16
11b CDCN (singlet) ⫺131.372322 1911 16.92
11c CH13CN (singlet) ⫺131.370283 1880 12.95
11d CHC15N (singlet) ⫺131.370218 1909 14.23
12a CHCN (triplet) ⫺131.412523 1749 28.38 1735p
1750q
12b CDCN (triplet) ⫺131.414770 1738 29.15 1730p
1740q
12c 13
CH CN (triplet) ⫺131.412688 1703 26.47 1698p
12d CHC15N (triplet) ⫺131.412610 1734 28.84 1718p
13
CCN ⫺130.750678 2033 109.98 1924r
14a CH3NC ⫺132.684955 2245 138.90 2166s ms
2161s ss
14b CD3NC ⫺132.694612 2243 132.49
14c CH3N13C ⫺132.685080 2206 136.77
14d CH315NC ⫺132.685095 2204 131.99
⫺
15a CH2NC ⫺132.078646 2084 192.48
⫺
15b CD2NC ⫺132.084306 2080 200.33
⫺
15c CH2N13C ⫺132.078787 2047 185.11
⫺
15d CH215NC ⫺132.078771 2047 187.03
16 2⫺
CHNC ⫺131.259164 1815 2756.19
17 3⫺
CNC ⫺130.295589 1520 6486.99

* The frequency values, used in the correlation (Fig. 2) are given in bold.
a
Gas phase [7].
b
Gas phase [8].
c
Gas phase [9].
d
Gas phase [10].
e
Gas phase [11].
f
Gas phase [12].
g
Ar matrix [13].
h
Solvent DMSO, counter ion K⫹ [1]. This value coincided with our measurements under the same conditions.
i
Our data, solvent water, counter ion K⫹.
j
Gas phase [15].
k
Gas phase [6].
l
Solvent hexamethylphosphor triamide, counter ion Na⫹ [4].
m
Solvent tetrahydrofurane, counter ion Na⫹ [4].
n
Solvent DMSO, counter ion Li⫹ [3].
o
Solid, in nujol [2].
p
Ar matrix [5].
q
N2 matrix [16].
r
Gas phase [6].
s
Gas phase [17].

1318 INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY DOI 10.1002/qua VOL. 106, NO. 6
 STUDIES ON IR SPECTRA AND STRUCTURE OF NITRILES, THEIR ANIONS, AND RADICALS

TABLE II ______________________________________
DFT calculated gas-phase deprotonation energies
(kJ molⴚ1) and literature pKa values for a series of
COH, NOH, and OOH acids.

pKa pKa
D
No. Compounds Ecorr (DMSO) (H2O)

1 CH3CN 1546.33 31.3a —

2 HCN 1457.43 12.9b 9.1b
3 CH2(CN)2 1425.02c 11.0a 11.9b
4 C6H5CH(CN)2 1345.77d 4.2b —
5 C6H5CH2CN 1491.07c 21.9a —
6 4-HOC6H4CN 1402.11e 13.1e 7.97e
7 3-HOC6H4CN 1423.03e — 8.61e
8 Barbituric acid 1345.25f 8.4a 4.08g
9 5,5-Diethylbarbituric 1424.75f 13.0a 8.00g
acid FIGURE 2. Correlation between theoretical [B3LYP
6-31⫹⫹G(d,p)] and experimental ␯CN of the species
a
Ref. [43]. studied.
b
Ref. [44].
c
Refs. [34] and [45].
d
Ref. [34]. to the formation of the strong hydrogen bonds of
e
Ref. [37]. water molecules with localized anions [44]), the
f
Ref. [46].
g
Ref. [47].
“correlation” with pKa (solvent water) is very
rough (R ⫽ 0.78) and cannot be used for practical
purposes.
The ED values of a small series of Broensted acids
are compared with literature pKa data in Table II SPECTRAL ANALYSIS
and Figure 1. We can see in Figure 1 that the cal-
culated gas-phase ED correlate fairly well (0.90 ⬍ The comparison between theoretical and experi-
R ⬍ 0.95) with pKa, measured in DMSO. The largest mental ␯CN of the species studied (Table I, Fig. 2)
deviations correspond to hydrogen cyanide (4.8 shows that these values correlate satisfactorily (0.95 ⬍
pKa units), barbituric acid (⫺3.6) and acetonitrile R ⬍ 0.99). This correlation is close in relative accuracy
(⫺3.4). In contrast, (as can be expected, due mainly to a similar correlation found [48] for large series (R ⫽
0.9723, n ⫽ 80) nitriles and their anions (without rad-
icals). However, the ␳ (slope) value of the cited corre-
lation (0.7256 [48]) differs strongly from ␳ (Fig. 2), due
to the differences in the theoretical methods used (ab
initio Hartree–Fock (HF) 6-31G [48] and B3LYP
6-31⫹⫹G(d,p) in this work). The correlations obtained
could be used for an approximate prediction of un-
known ␯CN of molecules, anions, and radicals, con-
taining cyano groups.
In a qualitative agreement between theory and
experiment (as well as with the data in the literature
[41, 45, 49 –51]), the conversion of nitrile molecules
into anions and radicals leads to strong decreases in
␯CN (calculated down to 615 cm⫺1, measured down
to 509 cm⫺1) and strong increases in ACN (calcu-
lated up to 60.8-fold, measured up to 60.1-fold,
Table I). We should mention that further more
FIGURE 1. Correlation between DFT deprotonation “dramatic” ACN increases are known: 102-fold for
energies and pKa (solvent DMSO) for a series of COH, the malononitrile carbanion [45, 51] and 136-fold
NOH, and OOH acids. for the phenylmalononitrile carbanion [34].

VOL. 106, NO. 6 DOI 10.1002/qua INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY 1319
GEORGIEVA AND VELCHEVA

TABLE III _____________________________________________________________________________________________

Gas-phase theoretical [B3LYP 6-31ⴙⴙG(d,p)] and experimental (literature data, bold, in parentheses) bond
lengths (Å), and angles (degrees) of the molecules, anions, and radicals studied.

Species r(C'N) r(COC) r(COH) r(NOH) ⬍HCN ⬍HNC ⬍HCC ⬍CCN

HCN 1.155 — 1.063 — 179.8 — — —

(1.153)a — (1.066)a — (180.0)a — — —
HNC (singlet) 1.189 — — 1.031 — 179.7 — —
CN⫺ 1.184 — — — — — — —
CN• 1.174 — — — — — — —
CH3CN 1.161 1.461 1.094 — — — 110.2 179.9
(1.157— (1.458– (1.094– (109.5–
1.159)c 1.468)c 1.107)c — — — 110.0)c (180.0)c
CH3NC 1.175 1.422d 1.093 — — — 109.2e —
(1.167)b (1.427)b,d (1.094)b — — — (109.5)b,e —
⫺
CH2CN 1.191 1.384 1.085 — — — 120.6 180.0
2⫺
CHCN 1.223 1.374 1.106 — — — 114.9 179.3

CH2CN 1.177 1.384 1.084 — — — 120.1 179.9
CHCN (triplet) 1.214 1.294 1.068 — — — 169.6 177.6

CCN 1.189 1.372 — — — — — 175.0

a
Gas phase [53].
b
Gas phase [54].
c
Gas phase [55].
d
r(CON).
e
⬍HCH.

In fact, the lowest ␯CN frequencies (ⱕ1900 cm⫺1,
Table I) should be considered as ␯CCN
as
. According to
the calculations, the ␯CN vibrations of nitriles al-
ways include participations of the next ␯CC coordi-
nates, e.g., 9:1 (by energy) for the acetonitrile mol-
ecule. However, in the case of very low ␯CN, the
participations of ␯CN and ␯CC coordinates become
comparable by energy: the two chemical bonds be-
come partially double (cf. the CC and CN bond
lengths in Table III), and the corresponding coordi-
nates interact strongly with each other.
Again, in agreement between theory and exper-
iment, the isotopic shifts caused by 13C are usually
larger than that of 15N (Table I). The calculated
deuterium isotopic shift for DCN is 192 cm⫺1 and
the measured one is 83 cm⫺1; for DNC, theoretical
113 cm⫺1, experimental 89 cm⫺1. The high isotopic
shift values in these cases can be explained by the
strong coupling between adjacent ␯DOC and ␯CN
(␯NC) coordinates; this kind of coupling is obviously
impossible in acetonitrile and its derivatives.
STRUCTURAL ANALYSIS
The experimental (found in the literature) and
theoretical bond lengths and bond angles of the
species studied are listed in Table III. We can see
from the comparison that the theoretical structural
parameters of HCN, CH3CN, and CH3NC practi-
cally coincide with the experimental ones. The
mean absolute deviation between them is 0.0034 Å
for the bond lengths and 0.25° for the bond angles.
The agreement is excellent, including for r(COH),
as the experimental data correspond to the gas
phase and are free of the decrements, typical for the
x-ray data [52].
To confirm our statement about the good struc-
tural description of the species studied by the
B3LYP 6-31⫹⫹G(d,p) method, we should mention
that the calculated dipole moment ␮ of acetonitrile
(4.077 D) is close to the experimental values of
3.92–3.96 D [55, 56] determined in the gas phase.
Similar (i.e., very good) are the results for hydrogen
cyanide: calculated 3.064 D, measured 2.957–3.00 D
[57–59].
Conclusion
The comparisons, performed in this work be-
tween experimental (in cases they are available)
and theoretical data, showed good agreement (for

1320 INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY DOI 10.1002/qua VOL. 106, NO. 6
 STUDIES ON IR SPECTRA AND STRUCTURE OF NITRILES, THEIR ANIONS, AND RADICALS
the IR frequencies) and very good agreement (for
the structural parameters) of the simplest nitriles
(C1 and C2) and a large series of their anions and
radicals.
ACKNOWLEDGMENTS
The authors thank Professor I. G. Binev, D. Sc,
for the useful discussion.
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1322 INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY DOI 10.1002/qua VOL. 106, NO. 6