Journal of Molecular Structure (Theochem) 617 (2002) 149–168

www.elsevier.com/locate/theochem

Hyperfine coupling constants and electron-spin g-factors of the

þ þ
isovalent radicals C2
2 , Li2C2 , linear CCX (X ¼ H, Li, Be ), and
bent C2X (X ¼ Li, Na, Beþ, Mgþ). An ab initio studyq
Pablo J. Bruna, Friedrich Grein*
Department of Chemistry, University of New Brunswick, Fredericton, NB, Canada E3B 6E2
Received 12 June 2002; accepted 27 June 2002

Abstract
This theoretical work reports the hyperfine coupling constants (hfcc) and electron-spin g-factors for the title radicals. The
hfccs are evaluated using density functional theory methods and extended basis sets. The electron-spin resonance (ESR)
parameters for CCH reproduce the experimental results; the same is expected for the remaining radicals, for which experimental
þ
data are not yet available (except bent MC2). Aiso(13C) ranges from 40 to 85 MHz for C2 2 ; Li2 C2 and bent LiC2/NaC2, and
145– 240 MHz for bent BeCþ 2 =MgC þ
2 ; indicating that the s(C) spin-densities are not higher than 8%. For each of these systems,
Adip(C) is close to the atomic value (< 54 MHz), as expected for p-type SOMOs. The g-shifts are evaluated using perturbation
theory up to second order, MRCI wavefunctions, and 6-311þþG(2d,2p) basis sets. The average g-shift (kDgl) is positive for
linear CCX (up to 420 ppm), as the magnetic coupling with the low-lying excitation p ! s ( positive contribution) surpasses
that with the higher-lying s ! pp (negative ). By contrast kDgl is negative for the remaining systems, about 2 900 ppm for C2 2 ;
Li2 Cþ
2 (only s ! p p
contributes), and from 2315 to 2 665 ppm for the C2v species MC 2 (s ! p p
dominates but p ! s is also
contributing). Our results for bent LiC2 and NaC2 suggest that the ESR spectra attributed to them should actually belong to other
(unidentified) radicals since (i) a theoretical Aiso ðCÞ < 77 MHz for NaC2 is substantially smaller than <290 MHz estimated by
combining Adip ðCÞ < 54 MHz with the experimental A’(C) and (ii) the theoretical kDgls are negative—in accord with a
positive spin-rotation coupling constant in C2 2 —but at variance with the positive kDgls reported experimentally. q 2002
Elsevier Science B.V. All rights reserved.
Keywords: C2 2 -type radicals; Hyperfine coupling constants; Electron-spin resonance g-factors; Ab initio calculations; Density functional
calculations; Comparison with experimental results

1. Introduction (ESR) spectra for the isovalent radicals C2H [1] and
Mþ C2 2 (M ¼ Li, Na, K) [2] trapped in Ar matrices.
2 þ
About 30 years ago, Graham, Dismuke and The ESR spectrum of C2 2 ðX Sg Þ could not be
Weltner (GDW) measured the electron-spin resonance detected in the absence of alkali-metal cations. From
these studies on 9 valence electron (VE) systems, they
q
In honour of William J. Meath assigned a linear structure with an X2Sþ ground state
* Corresponding author. Tel.: þ1-506-453-4781; fax: þ 1-506-
453-4981. (GS) to C2H but a bent C2v structure with an X2A1
E-mail address: fritz@unb.ca (F. Grein). state to Mþ C22 :

0166-1280/02/$ - see front matter q 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 1 6 6 - 1 2 8 0 ( 0 2 ) 0 0 4 2 4 - 4
150 P.J. Bruna, F. Grein / Journal of Molecular Structure (Theochem) 617 (2002) 149–168
GWD found the electronic g-tensor of C2H to be
isotropic ðgk ¼ g’ Þ; with an average g-shift (kDgl) of
200 ^ 500 ppm ranging from negative to positive
values. Shortly thereafter, Adrian and Bowers [3]
determined kDgl to be 370 ^ 50 ppm in Ar but
2 570 ^ 50 ppm in Kr matrices. Similarly, Jinguji
et al. [4] obtained a negative kDgl from their work in
Kr matrices (2 300 ^ 50 ppm). Thus, kDgl of trapped
C2H is small, but its sign depends on the matrix used.
Most likely, however, the average g-shift of free C2H
is positive, as shown next.
For linear 2Sþ species, kDgl and Dg’ should have
the same sign (since Dgk is small). On the other hand,
according to Curl’s expression Dg’ ¼ 2g=2B [5]
(where g and B are the spin-rotation coupling and
rotational constants), Dg’ of gas-phase C2H is about
þ 720 ppm (using Curl’s formula), i.e. positive since
the experimental g is negative [6,7]. Assuming Dgk <
2150 ppm; it follows that kDgl of free C2H should be
about 430 ppm, close to the Ar matrix results.
GDW’s work on bent LiC2 and NaC2 gave a
positive kDgl of about 3700 ppm. However, studies
from this laboratory reported kDgl for the X2A1 GS of
both radicals to be negative and small
(< 2 300 ppm); the reasons for kDgl to have such a
sign have been discussed in Refs. [8,9]. In short, due
to the existence of well-defined ion-pairs Mþ C2 2 ; kDgl
of bent MC2 should have the same sign as for C2 2 ; and
a comparable magnitude.
2 þ
For C2 2 ðX Sg Þ; theoretical studies [8,9] find -
Dgk ¼ 2160; Dg’ ¼ 21166; and kDgl ¼ 2831 
ppm: A calculated Dgk , 0 is not only in line with an
experimental g . 0 for free C2 2 [10] but also the
theoretical value is in excellent agreement with Curl’s
estimate (2 1216 ppm). These C2 2 results support our
negative kDgl assigned to Mþ C2 2
2 ðX A1 Þ; at variance
with experiment.
The causes for the discrepancy are unclear. As a
possible explanation, the g-tensors for the 12B1
excited states of bent LiC2 and NaC2—formally p-
states having positive kDgls—were also calculated,
giving kDgls of 3500 ppm [8,9]. Although close to the
experimental result, it is nevertheless difficult to
rationalize how those excited states might have such
unusually long lifetimes for their ESR spectra to be
detected.
Knowledge of the hyperfine coupling constants
(hfcc) may provide additional information to solve
the puzzle. After 13C isotope substitution, GWD [2]
assigned to A1 < A2 ðA’ Þ of Naþ C2 2 a value of
233 MHz, whereas the A3 ðAk Þ component (masked
by C2H lines) could not be resolved, i.e. Aiso and Adip
are experimentally unknown for C. Although all hfccs
were determined for the metal atoms (mostly Mþ
though), they are per se of little help to identify the
counter-anion unequivocally.
Theoretical hfccs reported for C2H [11,12] are in
good accord with experiment. The corresponding g-
tensor, however, has not yet been studied theoreti-
cally, so that it is not clear why kDgl is positive. The
situation for C2 2 ; LiC2 and NaC2 is exactly the
opposite: theoretical data are available for the g-
tensors but not for the hfccs. The latter constants could
establish whether the X2A1 or the 12B1 states—and
for that matter, whether MC2 radicals at all—had
actually been the carriers of the ESR spectra recorded
by GDW.
In brief, the current knowledge about the ESR
parameters of the C2 2 ; C2H and MC2 radicals is
fragmentary. To remedy such situation, we have
calculated the hfccs and g-factors for several 9VE
radicals containing a C2 unit. Our main interest is to
find trends in the hyperfine (hf) parameters for a series
of related compounds.
The complete list of radicals, of which six have
never appeared in the literature, includes the ðD1h Þ
2 þ
X2 Sþ 2
g anion C2 ; the linear (C1v)X S species C2H,
þ 2
LiC2 and BeC2 ; the bent (C2v)X A1 systems LiC2,
NaC2, BeCþ þ
2 and MgC2 ; the trapezoidal (D2h)X Ag
2
þ 2 þ
cation Li2 C2 ; and the (C1)X A HC2Li radical with
a skewed conformation. The g-data for C2 2 and bent
LiC2, NaC2 will be taken from our previous reports
[8,9].
2. Technical details
The equilibrium geometries of the new species,
optimized at the MP2/6-311þ þ G(2df,2pd) level with
GAUSSIAN 98 [13], are given in Table 1. The (MP2)
vibrational frequencies (footnote b, Table 1) are all
real, indicating minima.
In all cases the CC bond is placed collinear with
the y-axis. For MC2(C2v) and M2 Cþ 2 ðD2h Þ; M lies
along z, and the x-axis is perpendicular to the
molecular plane.
 P.J. Bruna, F. Grein / Journal of Molecular Structure (Theochem) 617 (2002) 149–168 151

Table 1
Equilibrium geometries, atomic charges (q ) and spin-densities (SD) calculated for the present radicals

Radicala,b,c R(CC) (bohr) R(CX) (bohr) q(C)d q(X) SD(C)d SD(X)

X2 Sþ
g C2
2 2.397 20.5.0 0.5
2 þ
XS CCH 2.300 1.999 0.05/ 2 0.12 0.07 1.07/ 2 0.09 0.02
CCLi 2.274 3.629 20.07/ 2 0.17 0.24 0.88/0.07 0.05
CCBeþ 2.243 2.976 20.25/0.59 0.66 1.05/ 2 0.02 20.03
X2A1 LiC2 2.405 3.870 20.18 0.36 0.52 20.04
NaC2 2.415 4.522 20.26 0.52 0.52 20.04
BeCþ2 2.415 3.224 0.17 0.66 0.56 20.12
MgCþ 2 2.418 3.993 0.09 0.82 0.54 20.08
X2Ag Li2 Cþ
2 2.412 4.096 20.02 0.52 0.49 0.01
X2A HCCLiþe 2.396 2.030(H), 3.931(Li) 0.70/ 2 0.32 0.23(H), 0.61(Li) 0.62/0.42 20.01(H), 20.03(Li)
a
Experimental Re for C2 2 [40]; R values for CCH from Ref. [11]; other geometries optimized here.
b
Vibrational frequencies (cm21), with CC-stretching underlined: C2 2 ; 1781(sg), exptl. [xx ]; CCH, 1841; CCLi: 63(p), 637(s), 2447(s);
CCBeþ: 178(p), 1023(s), 2365(s); LiC2: 328(b2), 610(a1), 1787(a1); NaC2: 264(b2), 365(a1), 1742(a1); BeCþ 2 : 333(b2), 949(a1), 1735(a1);
þ
MgCþ þ
2 : 312(b2), 564(a1), 1739(a1); Li2 C2 : 229(b3u), 297(b3g), 427(ag), 484(b2u), 584(b1u), 1754(ag); HCCLi : 180, 474, 845, 2314, 3407,
3710(a). MP2 data.
c
Linear CCLi and CCBeþ lie 0.50 and 0.56 eV, respectively, above their bent (C2v) isomers.
d
First entry for terminal C.
e
\HCC ¼ 174:88; \CCLi ¼ 162:88; t ¼ 3:28:

All hf tensors of C2 2 ; linear CCX and trapezoidal
M2 C þ 2 are diagonalP the xyz coordinates, with Aii ¼
in
ðAiso þ Tii Þ and Tii ¼ 0 for each center ðii ¼
xx; yy; zzÞ: For C and X, Ak and A’ are also used
[14], with Ak ¼ ðAiso þ 2Adip Þ standing for Ayy ; and
A’ ¼ ðAiso 2 Adip Þ for Axx ; Azz ; here Adip ¼ Tyy =2 ¼
2Txx ¼ 2Tzz :
For bent MC2(C2v), the hf tensors for M are
diagonal in xyz but those for C are not, except for the
Axx component perpendicular to the molecular plane.
This is clearly seen by comparing the SOMO structure
in high (D1h, D2h) and low (C2v) symmetry.
þ
The SOMOs of C2 2 and M2 C2 are mainly of type
(py(C) 2 py(C)), with minor contributions from
(s þ s) on C and (s þ s)/(pz 2 pz) on M. In bent
MC2(C2v) radicals, however, the pu-type component
(pz(C) 2 pz(C)) of C2 2 also contributes to the SOMO,
and as a result, the in-plane hf (anisotropic)
components of C are not collinear with y and z
anymore. However, since the py/pz mixing is not too
strong, the new eigenvectors y0 , z0 do not differ much
from y, z (the angle of rotation about the x-axis will be
given in the tables). The diagonalized in-plane
components of the anisotropic term are here labeled
as T 0yy and T 0zz :
The hfccs Aiso and Adip (Txx ; T 0yy ; T 0zz ) are also
calculated with GAUSSIAN 98. The methods used
include UHF and four density functional theory
(DFT) methods (namely SVWN, B3LYP, B3PW91
and PW91PW91 [15 – 18]); MP2 and CISD results are
also given in some cases.
In general, the median of all DFT data will be taken
as best estimate of each hfcc, a procedure being justi-
fied by the results to be discussed later. Recent studies
[19,20] of the hfcc’s for 5VE radicals such as Bþ þ
2 ; Al2 ;
þ
Ga2 —all having 2sg SOMOs of type (py 2 py) like for
the present 9VE systems—have shown that the
actually calculated hfccs deviate slightly from the
corresponding median (average) values.
Several basis sets were used to investigate the
numerical stability of the hfccs (Aiso in particular).
They include:
1. P (Pople 6-311 þ G(2df) [21]): 12s6p2d1f/
5s4p2d1f for C, Li, Be; 13s10p2d1f/7s6p2d1f for
Na, Mg; and 6s2p1d/4s2p1d for H.
2. D (Dunning [22]): 10s6p2d1f/5s3p2d1f for C, Li,
Be; and 5s2p1d/3s2p1d for H.
3. S (Sadlej [23]): 10s6p4d(þ 1f)/5s3p2d1f for C, Li,
Be; 14s10p4d(þ 1f)/7s5p2d1f and 6s4p/3s2p for H.
152 P.J. Bruna, F. Grein / Journal of Molecular Structure (Theochem) 617 (2002) 149–168
4. C (Chipman [24]): 10s6p2d(þ 1f)/6s3p2d1f for C;
and 6s1p/4s1p for H.
5. B (Barone EPR-III [25]): 12s8p2d1f/8s5p2d1f for
C; and 7s2p/5s2p for H.
6. R (Roos ANO TZ [26]): 14s9p4d3f/5s4p3d2 for C,
Li, Be; 17s12p5d4f/6s5p3d2f for Na, Mg; and
8s4p3d/4s3p2d for H.
7. T (aug-cc-pVTZ [27]): 12s6p3d1f/5s4p3d1f for C,
Li, Be; and 6s3p2d/4s3p2d for H.
8. Q (aug-cc-pVQZ [27]): 13s7p4d3f2g/6s5p4d3f2g
for C, Li, Be; 7s4p3d2f/5s4p3d2f for H.
The electronic g-factor parameterizes the electron-
spin magnetic moment ms of a radical [13,28], with
ms ¼ 2mB g·S (mB is the Bohr-magneton, g a second-
rank tensor, and S the spin angular momentum). In
this work, we report Dgii-values, which are defined as
Dgii ¼ ðgii 2 ge Þ; where ge ¼ 2:002319 for a free-
electron.
We evaluate the g-shifts using perturbation theory
[28 – 30]. First (1st) order contributions are calculated
using the ROHF (GS) wavefunction. Those in second
(2nd) order are obtained as a sum-over-states (SOS)
expansion, in which the magnetic coupling of the GS
with a particular excited state is given by
Dg ¼ (SO·L)/DE. Here, SO and L are the matrix
elements of the spin –orbit coupling and magnetic
transition moment (angular momentum), and DE
represents the (vertical) excitation energy.
All g-shifts to be reported are diagonal in the xyz
system of coordinates (the g-shifts of HCCLiþ were
not studied). The type of excited states which couples
magnetically with the GS is determined by the point
group symmetry of the radical. However, not all
allowed states contribute significantly to a given Dgii.
In fact, of relevance are only those having a spin-
density (SD) distribution similar to that of the GS (to
give large SO and L ), and with DEs well below 10 eV.
Hence, the SOS expansions are generally dominated
by only a few terms [31].
Several of the g-shifts calculated here are gauge-
þ
independent, e.g. all Dgiis of C22 ; Li2 C2 ; Dgk of linear
CCX; and Dgzz of bent MC2. The remaining g-shifts
are evaluated by placing the origin of coordinates at
the corresponding electronic-charge centroid [32].
The SOS expansions are based on multireference
CI (MRCI) wavefunctions [33 – 39]. In all cases, 6-
311þ þ G(2d,2p) basis sets were used.
3. Results
Table 1, besides the equilibrium geometries, also
includes atomic charges (q ) and spin-densities (SD)
from Mulliken population analyses (B3LYP/6-
311þ þ (2df,2pd) data). For linear CCX, the terminal
and central C atoms are labeled as Ca and Cb, respec-
tively. Throughout this paper only VEs are labeled.
On average, R(CC) is about 2.3 bohr for linear
CCX, and 2.4 bohr for the nonlinear radicals,
practically retaining the experimental Re of C2 2
(2.397 bohr [40]).
As seen in Table 1, for all C2v radicals the SD on
each C is slightly above 0.5, and for Li2 Cþ2 (D2h) it is
slightly below, i.e. a well-defined C2
2 unit is present in
all these systems. For linear CaCbX, the open shell is
mostly localized at the terminal Ca atom, with
SD(Ca) < 1.0.
3.1. Hyperfine coupling constants Aiso and Adip
Tables 2– 8 summarize the hfccs calculated for the
most abundant isotope with non-zero nuclear mag-
netic moments, i.e. 1H, 7Li, 9Be, 13C, 23Na, 25Mg (the
moments are negative for Be and Mg). Dipolar terms
(Tii) are given in their principal axes.
Linear C2H(X2Sþ). The C2H radical will be
discussed first since a comparison with literature
data allows to assess the accuracy of our calculation
strategy.
Very encouragingly, the hfccs of C2H (Table 2)
fluctuate relatively little with changes in the con-
ditions of calculation. For example, according to all
results at the DFT level, Aiso(Ca) ranges from 940 to
1100 MHz, with a recommended median of 1000 ^
50 MHz covering 3/4 of the 20 calculated values.
As well, the basis set dependency is relatively
weak. Taking the B3LYP data as reference, Aiso(Ca)
(MHz) is 1046 with basis P (83 contracted AOs ),
1100 with D (81 ), 1075 with B (91 ), 1038 with T
(115 ) and 1065 with Q (206 ). In short, Aiso(Ca)s
calculated with the medium-size bases P to T (81 –115
AOs) do not differ substantially from those obtained
with the extended basis Q (206 ). Similar observations
apply to Aiso(Cb) and Aiso(H).
All Adips of C2H are even less sensitive to the
theoretical treatment, a behavior well documented in
the literature for numerous radicals [41].
 P.J. Bruna, F. Grein / Journal of Molecular Structure (Theochem) 617 (2002) 149–168 153

Table 2
Aiso and Adip values (in MHz) calculated for the CaCbH radical using different methods and basis sets
13 13 1
Method Basis set Ca Cb H

Aiso Adip Aiso Adip Aiso Adip

UHF P 1335 7 2 55 165 213

D 1362 10 20 53 147 211
B 1332 11 25 54 160 211
T 1263 11 60 53 151 211
Q 1317 11 46 54 153 211
SVWN P 952 51 206 24 45 3.9
D 1015 49 211 23 37 3.8
B 995 53 212 24 49 3.9
T 942 51 213 24 46 4.0
Q 965 53 216 24 47 4.0
B3LYP P 1046 50 219 25 54 3.2
D 1100 48 222 24 47 3.1
B 1075 51 224 26 59 3.2
T 1038 50 228 25 55 3.3
Q 1065 51 231 26 57 3.4
B3PW91 P 1019 47 212 27 58 2.3
D 1076 45 215 27 51 2.3
B 1050 48 216 28 63 2.4
T 1005 46 223 27 58 2.4
Q 1031 48 224 28 60 2.5

PW91PW91 P 981 50 211 25 56 3.5

D 1036 52 215 24 48 3.4
B 1017 52 216 26 62 3.5
T 973 50 220 25 57 3.5
Q 994 52 222 26 59 3.6

Best estimate 1000 ^ 50 50 ^ 2 218 ^ 5 25 ^ 1 53 ^ 5 3.3 ^ 0.5

Expt ESR [1] 902 ^ 1 39 ^ 1 156 ^ 1 17 ^ 1 44 ^ 1 4^1
Rotation (13CCH) [7] 939.0(11) 44(48) 49.4(21) 4
(C13CH) 177.9(20) 6.3(24) 55.5(11) 4
Theory MRDCI [11] 993(882) 47.5 211(153) 19.7 44.6(39) 4.15
Hybrid DFT-MD [12] 935 173 42

Our best estimates for Ca, Cb and H (Aiso ¼
1000 ^ 50; 218 ^ 5, 53 ^ 5 MHz, and Adip ¼ 50 ^
2; 25 ^ 1, 3.3 ^ 0.5 MHz, respectively) are close to
the experimental values (Table 2), which leads us to
believe that the hfccs calculated for other radicals are
of similar accuracy.
The present results are also in line with those from
previous ab initio studies (Table 2). Eriksson and
Laaksonen (EL) [12] calculated Aiso(C2H) with
various methods (UHF, MP2, QCISD, SVWN,
BLYP, BP86, PWP86, B3LYP, B3P86) and two
basis sets, 6-311G(d,p) and 6-311 þ G(2df,p). Our
work complements that of EL by using other DFT
methods as well (B3PW91 and PW91PW91), and a
large variety of extended basis sets.
EL found MP2 and QCISD to largely under-
estimate Aiso of Cb but overestimate that of the other
two centers. A similar conclusion can be drawn from
our MP2 and CISD results (not tabulated). Further, EL
noted that BLYP and BP86 give an average Aiso(Ca)
of 700 ^ 50 MHz, lying < 200 MHz below exper-
imental results. On the other hand, the Aiso medians
154 P.J. Bruna, F. Grein / Journal of Molecular Structure (Theochem) 617 (2002) 149–168

Table 3
Aiso and Adip values (in MHz) calculated for linear CCLi and CCBeþ using different DFT methods and basis sets
13 13 7
Method Basis set Ca Cb Li

Aiso Adip Aiso Adip Aiso Adip

Ca Cb LiðX 2 Sþ Þ
UHF P 911 26 41 48 30 0.1
D 952 24 41 47 32 0.1
S 949 24 46 47 32 0.2
SVWN P 405 59 224 38 38 2.1
D 436 54 216 34 41 2.2
S 428 54 219 34 40 2.2
B3LYP P 519 60 3 38 34 1.8
D 546 56 8 35 37 1.8
S 543 56 7 34 35 1.9
B3PW91 P 508 58 4 38 31 1.7
D 538 54 9 35 33 1.7
S 532 54 9 35 33 1.7
PW91PW91 P 439 60 219 38 40 2.0
D 464 56 213 35 42 2.1
S 459 55 215 35 42 2.1
Best estimate 485 ^ 50 56 ^ 2 0 ^ 15 36 ^ 2 37 ^ 5 2 ^ 0.2

13 13 9
Ca Cb Be

Aiso Adip Aiso Adip Aiso Adip

Ca Cb Beþ ðX 2 Sþ Þ
UHF P 1257 16 92 46 232 20.7
D 1315 15 92 46 233 20.7
S 1301 14 96 46 234 20.8
SVWN P 946 55 164 24 219 20.8
D 1006 52 171 23 220 20.7
S 985 51 169 22 220 20.8
B3LYP P 1032 51 179 25 219 20.7
D 1083 49 186 24 220 20.7
S 1072 48 184 24 220 20.7
B3PW91 P 1007 51 180 27 218 20.8
D 1063 49 187 26 219 20.7
S 1046 48 185 25 219 20.7
PW91PW91 P 973 54 171 25 222 20.8
D 1024 52 178 24 223 20.7
S 1010 51 176 24 223 20.8
Best estimate 1020 ^ 50 52 ^ 3 178 ^ 5 24 ^ 2 220 ^ 2 20.7

from their SVWN, B3LYP and B3P86 data differ little
from those obtained here (Table I in Ref. [12]).
Interestingly, EL simulated the thermal motion of
CCH in Ar matrices at 4 and 40 K via DFT-molecular
dynamics calculations. While the free radical is linear,
it becomes slightly bent in the matrices. Lowering of
the symmetry leads to a better accord between the
calculated and experimental results, e.g. Aiso(Ca)
changes from 1043 to 935 MHz in passing from the
linear to the bent conformation, to be compared with
902 MHz measured in Ar matrix (4 K).
Perić et al. [11] investigated the potential surfaces
and several properties of the lowest-lying doublet
states of C2H at the MRDCI level. Their reported Aisos
 P.J. Bruna, F. Grein / Journal of Molecular Structure (Theochem) 617 (2002) 149–168 155

Table 4
Aiso and Adip values (MHz) calculated for 13 C2
2 using different methods and basis sets. Results listed as Aiso/Adip

Basis seta UHF MP2 SVWN B3LYP B3PW91 PW91/PW91

P [6-311 þ G(2df) (68 )] 238/60 46/48 37/50 34/54 8/54 29/52

P0 [6-311 þ G(3df) (78 )] 235/60 48/49 38/50 36/54 10/54 31/52
D [D95 þ G(2df) (60 )] 227/56 58/44 54/45 45/49 21/49 41/47
S [Sadlej (62 )] 230/56 59/44 46/45 42/49 16/49 37/47
C [Chipman (64 )] 227/56 58/44 51/44 45/49 20/49 41/47
B [EPR-III (80 )] 227/61 51/49 55/51 44/55 21/55 41/53
R [Roos (ANO) (78 )] 222/61 45/49 41/50 34/55 11/54 28/52
T [aug-cc-PVTZ (92 )] 226/60 53/48 44/50 45/54 20/53 41/51
Q [aug-cc-PVQZ (160 )] 244/61 41/49 33/51 32/55 5/55 27/53
Medianb 231/59 51/47 44/48 40/53 15/52 35/50
a
Number of contracted AOs in italics.
b
Best estimate: Aiso ¼ 40 ^ 10 and Adip ¼ 51 ^ 5 MHz (using SVWN, B3LYP and PW91PW91 data).

(Table 2) are essentially the same as our best estimate
for Ca and Cb (993 and 211 vs 1000 and 218 MHz)
but slightly smaller for H (44.6 vs 53 MHz). The
vibrationally corrected Aisos from Perić et al., i.e. 882,
153 and 39 MHz, lie close to the experimental values.
Linear LiC2 and BeC2þ ðX 2 Sþ Þ: The calculations on
linear LiC2 and BeCþ 2 ; summarized in Table 3, were
carried out using three medium-large basis sets only
(P, D, S), which, taking into account the C2H results,
are expected to give reliable hfccs. In general, the
Aiso(C)s obtained with SVWN and PW91PW91 are
slightly smaller than those using B3LYP and
B3PW91, a trend also observed for C2H.
The Aiso(C)s behave as expected from the SD data
(Table 1), that is, Aiso ðCa Þ @ Aiso ðCb Þ: However,
while the Aiso(C)s of BeCþ 2 (1020 for Ca and
178 MHz for Cb) are close to those of C2H (1000
and 218 MHz), they are much smaller in LiC2 (485
and < 0 MHz). It is also interesting that the average
Adips of 54 MHz for Ca and of 30 MHz for Cb in both
LiC2 and BeCþ 2 reveal little change with respect to
C2H (50 and 25 MHz).
The lAisols for Li and Be lie below 40 MHz.
Since the Aiso values for atomic 2S(s ) Li and Beþ
are about 365 and 2 610 MHz [14,42], respectively,
the s(M)-density in C2M is quite small (10%, or
less). Hence, the predominant charge distribution
corresponds to Liþ C2 2þ 2
2 or Be C2 :
2 2 þ
C2 ðX Sg Þ: The hfccs of this anion, given in
Table 4, have been studied with a variety of basis sets,
containing 60 2 160 contracted AOs. Regardless of
the DFT method, the Aisos obtained with the standard
bases P, P0 and R (68– 78 AOs) are again surprisingly
not too different from the value calculated with basis
Q (160 AOs), e.g. B3LYP gives < 34 MHz on
average. Other bases lead to Aisos about 10% higher
(B3LYP data, Table 4).
Considering all basis sets and correlated
methods together (except B3PW91), Aiso of C2 2
ranges from about 30 to 60 MHz, and Adip from 45
to 55 MHz, with the general tendency of Aiso to be
smaller than Adip. UHF delivers an erroneous
negative value for Aiso (like the CISD results, not
tabulated), whereas B3PW91 gives the correct sign
but underestimates this constant by more than 50%.
On the other hand, Adip(13C) again remains robust
against variations in the theoretical treatment.
The best estimates for C2 2 ; Aiso ¼ 40 ^ 10 and
Adip ¼ 51 ^ 5 MHz; are derived from the SVWN,
B3LYP and PW91PW91 data. The relatively large
error bar for Aiso ensures that most of the calculated
values are accounted for.
Since Aiso assigned to 2s of the C atom amounts to
3777 MHz [14], the rather small isotropic constant in
C22 indicates very little s-density, as expected for a
SOMO with a main (py 2 py) composition. Interest-
ingly, Adip of C22 is practically the same as that of Ca
in C2H (50 ^ 2 MHz, Table 2).
Bent LiC2, NaC2, BeC2þ and MgC2þ : The data for
LiC2/NaC2 and BeCþ þ 2
2 =MgC2 in their X A1 GSs are
listed in Tables 5 and 6. The results follow the same
behavior as observed for C2 2 and linear CCX: the
fluctuations are moderate for Aiso and rather small for
Adip.
156 P.J. Bruna, F. Grein / Journal of Molecular Structure (Theochem) 617 (2002) 149–168

Table 5
Aiso and diagonalized Tii values (MHz) calculated for X2A1 of LiC2 and NaC2 using different methods and basis sets
13 7
Method Basis set C Li

Aiso Txx =T 0yy =T 0zz Aiso Txx =Tyy =Tzz

LiC2
SVWN P 68 252/103/ 2 51 24.9 22.5/ 2 1.2/3.7
D 86 246/93/ 2 47 25.5 22.5/ 2 1.2/3.7
S 77 247/94/ 2 47 25.3 22.5/ 2 1.2/3.7
R 89 249/99/ 2 50 27.1 22.5/ 2 1.2/3.7
B3LYP P 86 253/110/ 2 57 28.3 22.4/ 2 1.7/4.1
D 98 249/101/ 2 52 28.9 22.4/ 2 1.7/4.1
S 93 249/101/ 2 52 28.3 22.4/ 2 1.7/4.1
R 102 251/105/ 2 54 29.6 22.3/ 2 1.7/4.0
B3PW91 P 63 253/109/ 2 56 27.4 22.3/ 2 1.7/4.0
D 77 249/101/ 2 52 28.1 22.3/ 2 1.6/3.9
S 70 249/102/ 2 53 27.8 22.3/ 2 1.7/4.0
PW91PW91 P 70 252/106/ 2 54 25.0 22.4/ 2 1.3/3.7
D 83 248/98/ 2 50 25.6 22.4/ 2 1.3/3.7
S 77 248/98/ 2 50 24.9 22.4/ 2 1.3/3.7
R 90 250/102/ 2 52 26.7 22.4/ 2 1.3/3.7
Best estimatea 85 ^ 15 250/102/ 2 52 27 ^ 2 22.4/ 2 1.5/3.9
(^2/ ^ 4/ ^ 2) (^0.1/ ^ 0.2/ ^ 0.3)
Expt (Ar) [2] 215.1 2.8/ 2 5.2/2.5
13 23
C Na

Aiso Txx =T 0yy =T 0zz Aiso Txx =Tyy =Tzz

NaC2
SVWN P 58 251/102/ 2 51 220.8 21.1/ 2 0.9/2.0
D 75 246/92/ 2 46 219.7 21.2/ 2 0.9/2.1
S 67 246/92/ 2 46 220.0 21.1/ 2 0.9/2.0
R 79 249/98/ 2 49 221.7 21.0/ 2 0.9/1.9
B3LYP P 70 253/109/ 2 56 221.0 21.9/ 2 0.6/2.5
D 83 249/100/ 2 51 220.5 21.9/ 2 0.6/2.5
S 77 249/100/ 2 51 220.8 21.9/ 2 0.7/2.6
R 86 251/105/ 2 54 221.3 21.6/ 2 0.3/1.9
B3PW91 P 47 253/109/ 2 56 219.8 21.8/ 2 0.5/2.3
D 62 249/101/ 2 52 219.4 21.7/ 2 0.5/2.2
S 55 249/101/ 2 52 219.7 21.7/ 2 0.6/2.3
PW91PW91 P 57 252/105/ 2 53 217.2 21.4/ 2 0.7/2.1
D 71 248/97/ 2 49 216.2 21.4/ 2 0.7/2.1
S 64 248/97/ 2 49 216.6 21.4/ 2 0.8/2.2
R 77 250/101/ 2 51 218.7 21.1/ 2 0.8/1.9
Best estimatea 70 ^ 15 250/101/ 2 51 220 ^ 2 21.6/ 2 0.6/2.2
(^2/ ^ 2/ ^ 4) (^0.2/ ^ 0.2/ ^ 0.4)
Expt (Ar) [2] 211.8 0.9/ 2 0.6/ 2 0.2
a 0
Angle (deg) between y and y axes: 15 ^ 1 for LiC2 and 19 ^ 1 for NaC2.

The best estimates of Aiso(C) are 85(^ 15), 70(^ 15), sp(C) hybridization increases in the triatomics, with
240(^ 20) and 145(^ 10) MHz for LiC2, NaC2, BeCþ 2 that for the cations being somewhat more pronounced.
and MgCþ 2 ; respectively. Compared with 40 ^ The best estimates for Adip(C)s given in Tables 5
10 MHz for diatomic C2 2 ; the Aisos above indicate that and 6 have practically the same value, i.e. T 0yy <
 P.J. Bruna, F. Grein / Journal of Molecular Structure (Theochem) 617 (2002) 149–168 157

Table 6
Aiso and diagonalized Tii values (MHz) calculated for bent BeCþ þ
2 and MgC2 ; using different methods and basis sets

13 9
Method Basis set C Be

Aiso Txx =T 0yy =T 0zz Aiso Txx =Tyy =Tzz

BeC2þ ðX 2 A1 Þ
UHFP P 425 249/122/ 2 73 11.8 0.3/5.4/ 2 5.7
D 450 246/118/ 2 72 12.4 0.3/5.4/ 2 5.7
S 442 246/118/ 2 72 12.4 0.3/5.4/ 2 5.7
CISD P 240 251/113/ 2 62 16.1 0.9/3.0/ 2 3.9
D 260 248/108/ 2 60 17.0 0.9/2.9/ 2 3.8
S 251 248/107/ 2 59 17.7 0.9/2.9/ 2 3.8
B3LYP P 243 253/113/ 2 60 9.9 1.1/2.6/ 2 3.7
D 261 249/105/ 2 56 10.2 1.1/2.6/ 2 3.7
S 253 249/105/ 2 56 10.0 1.1/2.6/ 2 3.7
B3PW91 P 230 252/113/ 2 61 10.4 1.1/2.7/ 2 3.8
D 251 249/106/ 2 57 11.3 1.1/2.6/ 2 3.7
S 241 249/106/ 2 57 11.0 1.0/2.7/ 2 3.7
PW91PW91 P 205 252/109/ 2 57 7.5 1.3/2.1/ 2 3.4
D 222 248/101/ 2 53 7.6 1.3/2.1/ 2 3.4
S 213 248/102/ 2 54 7.3 1.3/2.1/ 2 3.4
Best estimatea 240 ^ 20 248/105/ 2 57 10 ^ 2 1.1/2.6/ 2 3.7
(^2/ ^ 4/ ^ 2) (^0.1/ ^ 0.2/ ^ 0.3)
13 25
C Mg

Aiso Txx =T 0yy =T 0zz Aiso Txx =Tyy =Tzz

MgC2þ ðX 2 A1 Þ
UHF P 247 250/120/ 2 70 20.5 20.3/3.1/ 2 2.8
S 260 248/116/ 2 68 20.6 20.3/2.8/ 2 2.5
CISD P 142 252/111/ 2 59 23.7 0.1/1.6/ 2 1.7
S 153 250/105/ 2 55 24.4 0.1/1.5/ 2 1.6
B3LYP P 157 254/112/ 2 58 15.0 0.1/1.5/ 2 1.6
S 168 250/104/ 2 54 14.9 0.1/1.4/ 2 1.5
B3PW91 P 139 253/111/ 2 58 15.8 0.1/1.5/ 2 1.6
S 149 250/104/ 2 54 15.7 0.1/1.4/ 2 1.5
PW91PW91 P 133 253/108/ 2 55 13.1 0.2/1.2/ 2 1.4
S 142 249/101/ 2 52 12.9 0.3/1.1/ 2 1.4
Best estimatea 145 ^ 10 251/107/ 2 56 15 ^ 2 0.1/1.4/ 2 1.5
(^2/ ^ 4/ ^ 2) (^0.1/ ^ 0.2/ ^ 0.3)
a
Angle (deg) between y0 and y axes: 15 ^ 1 for BeCþ þ
2 and 18 ^ 1 for MgC2 :

2Adip < 101 – 107 MHz: As well, they are not too
different from those for C22 and linear C2X. Obviously,
such a constancy in Adip(C) reflects the fact that we are
dealing with SOMOs primarily of p-character.
The s SDs at the metal centers are small, as pointed
out by lAisol values not higher than 20 MHz; as
expected, the corresponding Adips are even smaller
(Tables 5 and 6). The largest component, along the z-
axis, is positive in both radicals.
The hfccs calculated for the excited state 12B1 of
LiC2 and NaC2 are summarized in Table 7, and
compared with those of the X2A1 GS at their
corresponding equilibrium geometries (basis set: 6-
311 þ G(2d)). The methods used (CISD, QCISD,
CCD, MP2 and MP4(SDQ)) are not necessarily the
most suitable ones for the calculation of reliable
isotropic hfccs, but good enough to get a semiquanti-
tative picture about the decrease in Aiso when passing
158 P.J. Bruna, F. Grein / Journal of Molecular Structure (Theochem) 617 (2002) 149–168

Table 7
Aiso and diagonalized Tii values (MHz) calculated for the X2A1 and 12B1 states of bent LiC2 and NaC2
13
Method C X atom

Aiso Txx =T 0yy =T 0zz Aiso Txx =T 0yy =T 0zz

LiC2
X2A1 UHF 126 248/113/ 2 65 7.9 23.8/ 2 2.2/6.0
CISD 72 252/115/ 2 63 220.2 22.1/ 2 2.1/4.2
QCISD 76 244/92/ 2 48 0.4 22.6/ 2 1.6/4.2
CCD 54 254/116/ 2 62 225.8 22.1/ 2 2.0/4.1
MP2 51 258/129/ 2 71 248.5 21.8/ 2 1.0/2.8
MP4(SDQ) 61 254/118/ 2 64 230.9 22.0/ 2 1.6/3.6
(Median) (73) (252/114/ 2 62) (· · ·) (22.4/ 2 1.8/4.2)
12B1 UHF 2 68/ 2 31/ 2 37 26.2 21.2/ 2 3.1/4.2
CISD 2 72/ 2 32/ 2 39 26.1 21.3/ 2 3.0/4.3
QCISD 3 72/ 2 32/ 2 40 26.2 21.3/ 2 3.0/4.3
CCD 4 71/ 2 32/ 2 39 26.1 21.3/ 2 3.0/4.3
MP2 (14)a 74/ 2 33/ 2 41 27.8 21.3/ 2 3.1/4.4
MP4(SDQ) 4 72/ 2 32/ 2 40 26.1 21.3/ 2 3.0/4.3
(Median) (3) (72/ 2 32/ 2 40) (26.6) (21.3/ 2 3.0/4.3)

NaC2
X2A1 UHF 89 246/109/ 2 63 22.8 25.4/ 2 1.9/7.3
CISD 56 251/113/ 2 62 236.1 22.2/ 2 0.1/2.3
QCISD 61 238/85/ 2 47 20.4 22.0/ 2 1.5/3.5
CCD 45 252/112/ 2 60 245.6 22.1/ 2 0.2/2.3
MP2 50 257/127/ 2 70 288.5 21.0/ 2 0.3/1.3
MP4(SDQ) 52 253/117/ 2 64 256.3 21.4/0.4/1.0
(Median) (59) (250/111/ 2 61) (· · ·) (22.4/ 2 0.6/3.0)
12B1 UHF 2 69/ 2 32/ 2 37 217.1 1.1/ 2 2.2/1.1
CISD 2 70/ 2 33/ 2 37 213.7 1.1/ 2 2.2/1.1
QCISD 3 73/ 2 33/ 2 40 214.2 1.0/ 2 2.2/1.2
CCD 4 71/ 2 32/ 2 39 212.6 1.0/ 2 2.2/1.2
MP2 (14)a 74/ 2 33/ 2 41 216.3 1.0/ 2 2.2/1.2
MP4(SDQ) 4 73/ 2 33/ 2 40 213.4 1.0/ 2 2.2/1.2
(Median) (3) (72/ 2 33/ 2 39) (214.6) (1.0/ 2 2.2/1.2)

6-311 þ G(2d) basis set.

a
Not considered for averaging.

from a s-type (X2A1) to a p-type (12B1) state. No
DFT results are given because calculations starting
with the appropriate 1B1 UHF determinant collapse,
by default, into the GS. The medians in Table 7 are
based on the four correlated values of each hfcc (MP2
excluded).
For LiC2, Aiso(C) amounts to about 3 MHz in the
excited state vs 73 MHz in the GS (in reasonable
accord with 85 MHz at the DFT level, Table 5).
Regardless of the correct value for Aiso of 12B1,
which might be as high as 15 MHz or so, theory
confirms expectations, i.e. the s(C)-density is smaller
for 12 B1 ð1b1 3a21 Þ than for X2 A1 ð1b21 3a1 Þ: A similar
picture holds for NaC2, with the excited state
practically having no s(C)-density.
On average, Adip(C) of a given state is the same for
both radicals (and close to the DFT data for the GSs,
Table 5). For C in 12 B1 ð1b1 3a21 Þ; it holds now that
Txx ¼ 2ðT 0yy þ T 0zz Þ < 2Adip since the 1b1 SOMO
corresponds to px þ px; in general, these dipolar
contributions are smaller than for the GS, by about
0
30% when comparing Txx(12B1) with Tyy (X2A1).
þ
Li2 C2 cation. Table 8 collects the hfccs, together
with the g-shifts.
B3PW91 assigns to Aiso(C) an average value of
about 33 MHz, whereas other methods find Aiso(C) <
 P.J. Bruna, F. Grein / Journal of Molecular Structure (Theochem) 617 (2002) 149–168 159

Table 8
Hyperfine parameters (MHz), and MRCI values of DE (eV), SO (cm21), L (a.u.) and Dg (ppm) for Li2 Cþ
2

13 7
Method Basis set C Li

Aiso Adip Aiso Txx =Tyy =Tzz

UHF P 224 61 20.7 22.3/ 2 0.9/3.2

D 212 58 21.2 22.3/ 2 0.9/3.2
S 217 59 21.1 22.3/ 2 0.9/3.2
SVWN P 52 53 5.1 22.4/ 2 0.8/3.2
D 70 48 5.1 22.4/ 2 0.8/3.2
S 61 49 5.1 22.4/ 2 0.8/3.2
B3LYP P 50 57 4.4 22.3/ 2 0.9/3.2
D 62 52 4.3 22.3/ 2 0.8/3.1
S 57 52 4.5 22.3/ 2 0.9/3.2
B3PW91 P 26 56 3.8 22.3/ 2 0.8/3.1
D 40 52 3.7 22.3/ 2 0.8/3.1
S 33 52 3.8 22.3/ 2 0.8/3.1
PW91PW91 P 47 55 5.1 22.3/ 2 0.8/3.1
D 60 50 5.1 22.3/ 2 0.8/3.1
S 54 50 5.1 22.3/ 2 0.8/3.1
Best estimate 51 ^ 10 52 ^ 4 4.6 ^ 0.5 22.3/ 2 0.8/3.1
Dgxx Dgyy Dgzz

DEa 5.208 7.528 6.688

SOa 12.436 1.062 14.646
La 20.987 20.035 21.042
Dga 21168 22 21132
(2–6)b Dg 2121 1 219
S (2nd) 21289 21 21151
1st 2178 2208 2139
Dg Totalc 21467 2209 21290

6-311 þ G(2d) basis for g-shifts.

a
Parameters for first excited state. See Table 13 for coupling states.
b
Higher excited states.
c
kDgl ¼ 2990 ppm:

57 MHz. As usual, Adip(C) changes little with
theoretical treatment. The recommended values for
Li2 Cþ
2 ; Aiso ðCÞ ¼ 51 ^ 10 and Adip ðCÞ ¼ 52 ^ 4 
MHz; do not differ much from 40 ^ 10 and
50 ^ 5 MHz, respectively, assigned to C2 2 :
Aiso(Li) is positive and small (< 5 MHz), to be
compared with about 37 and 2 15 MHz for linear and
bent LiC2, respectively.
HCCLiþ cation. The Cs attached to H and Li are
labeled C1 and C2, respectively.
This system, which can be seen as generated by the
interaction of Liþ with linear CCH, has a skewed
geometry (C1) where \HCC and \CCLi are close to
1808; the corresponding dihedral angle t is rather
small (Table 1). In short, HCCLiþ has an almost linear
conformation.
The hfccs (not tabulated) were calculated with the
standard procedure (four DFT methods and the P, D, S
basis sets).
The 5a SOMO is a heavy admixture of pz/py
(pu/sg) on both C atoms, with pz (pu) dominating.
Indeed, the s-character is generally small, as pointed
out by Aiso values (MHz) of 22(^ 5) for C1, 44(^ 5)
for C2, 2 40(^ 5) for H and 2 9(^ 1) for Li. The
dipolar terms T 0zz for C1 and C2 (where the eigenvector
z 0 differs little from z ) are 93 and 80 MHz,
respectively; the corresponding values for H and Li
are smaller than 3 MHz.
160 P.J. Bruna, F. Grein / Journal of Molecular Structure (Theochem) 617 (2002) 149–168

3.2. g-Shifts addition, six 2P states can be generated by three

The g-shifts calculated for linear CCX compounds
are summarized in Table 9. Throughout this paper g-
shifts are given in ppm (ppm ¼ 1026).
For X2Sþ(1p43s) radicals with 9VEs, Dgk and
Dg’ are governed by the (2nd-order) magnetic
coupling with valence states of 2S2 and 2P sym-
metries, respectively.
In the present case, 2S2 states can only be generated
by double excitations with respect to the GS configur-
ation, resulting in extremely weak magnetic couplings.
In fact, for CCH the L values calculated for 2S2 states,
ranging from 7.5 to 10.5 eV, are not higher than 1025
a.u. Thus, Dgk is dominated by 1st-order contributions
(of about 2 165 ppm, ROHF data, Table 9), as simil-
arly observed for numerous other 2Sþ systems [14].
For linear CCX, several valence 2P states can be
generated by single excitations. Two of them have one
open-shell structure arising from the excitations
1p ! 3s and 3s ! 2p; they are expected to contrib-
ute positively and negatively to Dg’, respectively. In
configurations with three unpaired electrons each, i.e.
1p ! 4s (1p33s4s), 2s ! 2p (2s1p43s2p) and
1s ! 2p (1s1p43s2p). However, they are of minor
relevance for Dg’ due to their (expected) high DEs,
and the mutual cancellation between positive and
negative contributions from each pair of states.
Shih et al. [43] calculated the vertical electronic
spectrum of C2H up to about 11.5 eV. While
12P(A2P)(1p ! 3s) lies at about 0.6 eV vertically,
the 2P(3s ! 2p,s ! p p) state was placed at
< 10.7 eV. Other 2P states lying between both
extrema are either of Rydberg character (3s and 3py
are occupied rather than valence 4s(py þ py)) or
generated by the double excitation 1p2 ! 3s2p
(three 2P states); their magnetic couplings should be
rather weak.
In a first series of calculations using the 6-
311þ þ G(2d,2p) basis set containing diffuse AOs,
there was very little contribution from the 3s ! 2p
configuration in the first nine 2P states. In a second
series, a valence-only basis set was used, so that

Table 9
MRCI values of DE (eV), SO (cm21), L (a.u.) and Dg’ (ppm) for the X2Sþ state of linear CCH at three CC distances, and CCLI, CCBeþ at
equilibrium

g-Shifts CCH, DR ¼ R 2 Re CCLi CCBeþ

20.1 0 0.1

Dgk Total 2164 2163 2163 2163 2168

Dg’
12P(1p ! 3s) DE x 1.023 0.643 0.306 0.626 1.368
SO 4.289 4.052 3.828 3.450 3.789
L 0.490 0.434 0.456 0.385 0.406
Dg’ 1019 1481 2826 1053 558
2
P(mixed 3s ! 2p) DE 9.663 8.513 8.247 5.938 6.422
SO 6.663 7.716 5.509 4.089 6.310
L 20.452 20.589 20.439 20.347 20.494
Dg’ 2154 2249 2144 2119 2241
2
P(mixed 3s ! 2p) DE 9.917 10.516 9.915 7.539 9.963
SO 7.229 10.061 11.708 4.698 5.438
L 20.610 20.770 20.907 20.375 20.304
Dg’ 2220 2365 2531 2116 282
(Overall mixed 3s ! 2p contr.) Dg’ (2593)a (2614) (2675) (2520)b (2323)
Other 2Ps Dg’ 239 260 234 211 287
S(2nd) 387 807 2117 522 148
1st 294 292 292 264 259
Dg’ Total 293 715 2025 458 89
kDgl Isotropic 140 420 1300 250 <0
a
Dg’ ¼ 2219 ppm; higher 2P(mixed 3s ! 2p) state (DE ¼ 11:295 eV; SO ¼ 8:121 cm21 ; L ¼ 20:615 a:u:).
b
Dg’ ¼ 2285 ppm; higher 2P(mixed 3s ! 2p) state (DE ¼ 7:901 eV; SO ¼ 7:616 cm21 ; L ¼ 20:597 a:u:).
 P.J. Bruna, F. Grein / Journal of Molecular Structure (Theochem) 617 (2002) 149–168
the number of non-contributing (Rydberg) states is
considerably reduced. Now, the 3s ! 2p configur-
ation contributes to several high-lying 2P states
(Table 9) but its cumulative (negative) contribution
to Dg’ of 2 600 ppm is about half the value for C2 2 :
According to previous studies [11,43], the energy
separation between X2Sþ(1p43s) and 12P(1p ! 3s)
of C2H is relatively small ðTe < 0:41 eVÞ; and varies
strongly with Rcc, causing corresponding changes to
Dg’.
The variation of Dg’ was investigated for R ¼ Re
and R ¼ Re ^ 0:1 bohr: As seen by the potential
curves in Fig. 1 (which cover a larger DR range),
X2Sþ is crossed by A2P as Rcc increases, with the
latter state lying energetically lower at DR < 0:2 
bohr; i.e. Dg’ changes its sign in that region.
The SO and L values for the 12P coupling vary little
with Rcc (Table 9); similar findings were reported by
Perić et al. [44]. By contrast, DE changes drastically,
from about 1.02 to 0.31 eV. As a consequence, the
Dg’(12 P) contribution increases substantially
between the shortest and largest Rcc, i.e. from 1019
to 2826 ppm. On the other hand, the cumulative
contribution from higher excited states changes only
slightly (from about 2 630 to 2 710 ppm).
For linear CCLi and CCBeþ at their equilibrium
geometries, the SO and L values for 12P are close to
Fig. 1. CC-stretching potential curves for the X2Sþ and 12P states
of linear CCH. MRCI data.
161
those of C2H at Re (Table 9), with differences in
Dg’(12P) depending on the DE quantity, i.e. for
CCLi Dg’ is comparable to that of C2H but for
CCBeþ it is smaller (due to DE < 1:37 eV in the
cation vs < 0.63 eV in the neutral radicals).
In summary, the Dg’-values of these linear CCX
radicals are positive but small, since the coupling with
1p ! 3s (positive) is almost cancelled by that with
3s ! 2p (negative). For CCBeþ, kDgl is close to
zero, due to an increased DE and lower Dg’
(558 ppm) for 12P, and a substantial cumulative
negative contribution (2 410 ppm) from higher states
(Table 9).
We now focus our attention on the bent X2A1
radicals (Table 10). Trends expected for the g-shift
components of MC2 radicals with 9VEs have been
discussed earlier [8,9], and the reader is referred to
these papers for a more comprehensive analysis.
As pointed out by the SD data (Table 1), the pair
BeCþ þ 2
2 =MgC2 contains a C2 moiety, as does the pair
LiC2/NaC2. Hence, in the triatomics Dgzz[Dg’(i)] and
Dgxx[Dg’(o)] should be of similar sign and magnitude
as Dg’ ðC2 2 Þ (i and o stand for the in-plane and out-of
plane components). As seen in Table 10, this is indeed
the situation, with average values for all four MC2
systems of 2 1140(^ 100) for Dgzz and 2 740(^ 150)
ppm for Dgxx, both lying close to 2 1166 ppm for
Dg’ ðC2 2 Þ:
In all cases, these negative Dgs are governed by the
coupling with excited states related to the 2sg ! 1pg
excitation in C2 2 ; which in MC2 splits into 3a1 ! 1a2
and 3a1 ! 2b2 (Dgzz and Dgxx, respectively). In
general, lDgxxl is smaller than lDgzzl (Table 10) due
to the positive contribution from 2B2(1b2 ! 3a1)
[occupied MO ! SOMO].
The 1pu ! 2sg coupling, which is forbidden in
C22 ; is allowed in MC2, with a sizeable positive
contribution to Dgyy(Dgk) from 2B1(1b1 ! 3a1).
(Formally, this p ! s excitation is also respon-
sible for the positive Dg’ of linear CCX.) Since
the average DE(2B1) is 1.3 eV for the cationic but
0.8 for the neutral radicals, Dgyy(total) of BeCþ 2
and MgCþ 2 (83 and 541 ppm) is substantially
smaller than for LiC2 and NaC 2 (904 and
1072 ppm).
In summary, the kDgls of the present MC2(X2A1)
radicals are negative, with lkDgll being somewhat
larger for the cations, but in all cases smaller than that
162 P.J. Bruna, F. Grein / Journal of Molecular Structure (Theochem) 617 (2002) 149–168

Table 10
MRCI values of DE (eV), SO (cm21), L (a.u.) and Dgii (ppm) for the X2A1 state of bent MC2 radicals

g-Shifts BeCþ
2 LiC2a MgCþ
2 NaC2a

Dgyy[Dgk]
2
B1(1b1 ! 3a1) DE 1.433 0.886 1.118 0.766
SO 3.534 4.913 4.387 4.836
L 0.228 0.379 0.359 0.376
Dg 279 1071 200 1209
(7)2B1 Dg 221 216 26 24
S(2nd) 258 1055 726 1233
1st 2175 2151 2185 2161
Dgyy Total 83 904 541 1072
Dgzz[Dg’(i)]
2
A2(3a1 ! 1a2) DE 6.969 6.121 6.059 6.125
SO 14.402 10.819 9.635 11.559
L 20.978 20.886 20.663 20.933
Dg 21002 2798 2523 2897
(7)2A2 Dg 2101 2176 2498 4
S(2nd) 21103 2974 21021 2893
1st 2129 2147 2141 2162
Dgzz Total 21232 21121 21162 21055
Dgxx[Dg’(o)]
2
B2(1b2 ! 3a1) DE 2.779 2.559 2.634 2.548
SO 6.893 4.609 4.326 4.043
L 20.039 0.252 0.108 0.128
Dg 247 232 88 104
2
B2(3a1 ! 2b2) DE 4.521 5.165 5.189 4.895
SO 6.666 9.137 6.295 4.506
L 20.853 20.921 20.877 20.531
Dg 2624 2830 2528 2249
(6)2B2 Dg 230 253 104 2571
S(2nd) 2701 2577 2336 2716
1st 2142 2146 2164 2173
Dgxx Total 2843 2723 2500 2889
kDgl Isotropic 2665 2315 2375 2290

C2
2 (ab initio) [8,9]: Dgyy ¼ 2160 ppm; Dgxx, Dgzz ¼ 21166 pm; and kDgl ¼ 2830 ppm:
a
Refs. [8,9].

of C2 2 ; due to the positive component Dgyy in the
triatomics.
As seen in Table 8, the g-shifts calculated for
Li2 Cþ2 behave in the same way as for C2 : For
2
instance, Dgyy (parallel to the CC bond) is small and
negative (< 2 210 ppm), and described exclusively
by 1st-order contributions (a positive 2nd-order term
does not exist as in bent MC2). Also, Dgxx and Dgzz
(correlating with Dg’ ðC2 2 Þ) are governed each by the
coupling with the lowest-lying excited state with the
appropriate symmetry; their contributions, 2 1168
and 2 1132 ppm, essentially retain a Dg’-value of
2 1166 ppm as in C2 2 :
þ
In passing from C2 2 ðD1h Þ=Li2 C2 ðD2h Þ to
MC2(C2v), the inversion symmetry is lost. As a result,
in the triatomics Dgyy(Dgk) also has a positive 2nd-
order coupling between the sg-type SOMO and
occupied MOs with a pu-like structure (such coupling
is forbidden in D1h and D2h). On the other hand, the
pg ðC22 Þ components are less affected, in particular the
one perpendicular to the molecular plane of MC2 and
Li2 Cþ2:
Due to the above arguments, it is understandable
why the kDgls of Li2 Cþ 2
2 and C2 are similar
(< 2 900 ppm), and also larger than those of MC2
(2 290 to 2 665 ppm, Table 10).
 P.J. Bruna, F. Grein / Journal of Molecular Structure (Theochem) 617 (2002) 149–168 163

4. Discussion maintained, i.e. Aiso(C) should change little in passing

þ
from C2 2 to C2 to C2 : This is borne out by our values
Table 11 summarizes our calculated median values calculated for C2 (and Li2 Cþ
2
2 ; LiC2, NaC2 as well),
of Aiso(C), Adip(C) and kDgl, while Table 12 lists Aii, which span the same region as experimentally
the hf tensor components, in their principal axes. observed for C2 and Cþ 2 ; with all Aiso(C)s being
Except for the terminal C atom of linear CCX— smaller than 100 MHz.
where Aiso(C) has sizeable values from about 500 to On the other hand, Adip(C) has practically the same
þ
1000 MHz—other isotropic constants are substan- value for all systems in Table 11 from C2 2 to MgC2 ;
tially smaller (Table 11). In detail, Aiso(C) ranges from of about 52 MHz on average. For the C atom [14,47],
þ
40 to 85 MHz for C2 2 ; Li2 C2 ; LiC2 and NaC2, and Adip(C) is 108 MHz, which should become 54 MHz
from 145 to 240 MHz for BeCþ þ
2 and MgC2 : Taking when each C center of a given radical shares about
into account that for the C atom Aiso ¼ 3177 MHz one half of the spin-density, as is the case for the
[14], the s-density in these radicals is indeed small radicals in Table 1, except HC2Liþ and linear CCX.
(less than 8%). Altogether, the hfccs confirm that the SOMOs mainly
For the linear systems CCX, the s(Ca)-density is have a (py 2 py) composition.
< 15% for CCLi and 30% for both CCH and CCBeþ; At this point, it is of interest to compare the
the s-contribution to Cb, however, is also less than theoretical hfccs of NaC2 with their experimental
8%. As pointed out earlier (Section 3.1, and Table 2), counterparts. GWD reported A1 < A2 ðA’ Þ ¼
our results for CCH agree with experimental and other 233ð^22Þ MHz for 13C of NaC2; the A3 ðAk Þ com-
theoretical studies. ponent could not be determined. However, approxi-
The small Aiso(C)s predicted here for C2 2 and all mate values of Aiso(C) and Ak(C) can be obtained by
nonlinear radicals are indirectly supported by exper- combining Adip < 54 MHz with the experimental
imental studies on C2 and Cþ 2 : In detail, the Aiso(C) A’(C). For simplicity, we assume that the 3a1
values measured for a 3 Pu ð1p3u 2sg Þ of C2 [45] and for SOMO is exclusively (py 2 py), i.e. the largest
þ
X4 S2 2
g ð1pu 2sg Þ of C2 [46], namely 44(^ 9) and component of the hf tensor (Ayy) corresponds to Ak(C).
95(^ 1) MHz, respectively, show that their 2sg Since Aiso ¼ ðAk þ Adip Þ; and Ak ¼ ðA’ þ 3Adip Þ;
SOMOs also have very little s-character. for NaC2 one obtains Aiso(C) < 290 and Ak(C) < 390
In fact, the addition of one pu electron to 1p3u 2sg MHz. However, the theoretical values for the X2A1
of C2 formally leads to 1p4u 2sg of C2 2 ; while its GS are substantially smaller, Aiso ðCÞ ¼ 70ð^15Þ and
subtraction produces 1p2u 2sg of Cþ 2 : Certainly, the A0yy ½Ak ðCÞ ¼ 171ð^19Þ MHz (Tables 11 and 12), not
structure of the 2sg SOMO—mainly (py 2 py), as for supporting the experimental findings. Neither do the
most of the radicals studied here—is expected to be hf data for the p-type excited state 12B1, for which an
Aiso(C) value of about 7 MHz (Table 7) is, as
Table 11 expected, smaller than for the s-type GS.
Aiso , Adip and average kDgl calculated for the present radicals In short, the theoretical hfccs presented here,
together with the g-shifts reported earlier [8,9],
Radical Aiso(C)a (MHz) Adip(C)a (MHz) kDgl (ppm)
strongly suggest that the ESR spectra assigned by
C2 2 þ
2 ðX Sg Þ 40 50 2830 GDW to bent LiC2/NaC2 should actually belong to
Li2 Cþ 2
2 ðX Ag Þ 51 52 2990 other yet unidentified radicals. While the Dgs
LiC2 ðX2 A1 Þ 85 51 2315 calculated for the 12B1 excited states reproduce the
NaC2 ðX2 A1 Þ 70 51 2290 experimental findings, the corresponding hfccs do not.
BeCþ 2
2 ðX A1 Þ 240 52 2665
We now focus on the g-tensors. Table 13 lists the
MgCþ 2 ðX 2
A1 Þ 145 53 2375
CCHðX2 Sþ Þ 1000/218 50/25 420 symmetries of the excited states governing the Dgs,
CCLiðX2 Sþ Þ 485/0 56/36 250 and Table 14 the g-tensor components.
CCBeþ ðX2 Sþ Þ 1020/178 52/24 <0 The present 9VE radicals can be divided in two
HCCLiþ ðX2 A 22/44 93/80 Not calc. groups depending on the sign of kDgl, namely C2 2 ;
a
CCX and HCCLiþ: entries in the same order as in the first Li2 Cþ 2 and bent MC 2 having negative values (2 990 to
column. 2 290 ppm), and linear CCX having positive kDgls
164 P.J. Bruna, F. Grein / Journal of Molecular Structure (Theochem) 617 (2002) 149–168

Table 12
Hyperfine tensor components Aii (MHz) calculated for the present radicals, and comparison with available literature data

Radical Axx Ayy Azz

13
Ca CaCH(X2Sþ) TW 950(50) 1100(50) 950(50)
Ref. [11] 945 1088 945
Ref. [1]a 863(1) 980(1) 863(1)
CaCLi(X2Sþ) TW 429(52) 597(54) 429(52)
CaCBeþ(X2Sþ) TW 1124(56) 968(53) 1124(56)
13
Cb CCbH TW 193(6) 268(6) 193(6)
Ref. [11] 191.3 250.4 191.3
Ref. [1]a 139(1) 191(1) 139(1)
CCbLi TW 236(17) 72(19) 236(17)
CCbBeþ TW 154(7) 226(9) 154(7)
1
H CCH TW 50(6) 60(6) 50(6)
Ref. [11] 40.45 52.9 40.45
Ref. [1]a 41(1) 51(1) 41(1)
Ref. [3]a 42.3(3) 51.2(3) 42.3(3)
Ref. [7]a 40.2(4) 52.4(4) 40.2(4)
13
C C2
2 X2 Sþ
g 210(10) 140(10) 210(10)
Li2 Cþ2 X2Ag 21(14) 155(14) 21(14)
2
LiC2 X A1 35(17) 187(19) 33(17)
NaC2 X2A1 20(17) 171(19) 19(17)
BeCþ 2 X2A1 192(22) 345(24) 183(22)
MgCþ 2 X2A1 93(12) 253(14) 89(12)
LiC2 12B1 87(5) 217(5) 225(5)
NaC2 12B1 87(5) 218(5) 224(5)
NaC2 Ref. [2]a <233(20) Unresol.b <233(20)
7
Li LiC2 X2A1 29.4(2.1) 28.5(2.2) 23.1(2.3)
12B1 27.9 29.6 22.3
X2Sþ 35.0(5) 41.0(5) 35.0(5)
Ref. [2]a 212.3(6) 220.3(6) 212.6(6)
Li2 Cþ
2 X2Ag 22.3(5) 3.8(5) 7.7(5)
23
Na NaC2 X2A1 220.6(2.2) 221.6(2.2) 217.8(2.4)
12B1 213.6 216.8 213.4
Ref. [2]a 210.9(6) 212.4(6) 212.0(6)
9
Be BeCþ
2 X2A1 11.1 12.6 6.3
X2Sþ 221.4(2) 219.3(20) 221.4(20)
25
Mg MgCþ
2 X2A1 15.1 16.4 13.5

C2v radicals: Aii(C) in the corresponding principal axes (Tables 5 and 6).
a
Experimental.
b
About 390 MHz (estimated here assuming Adip ¼ 54 MHz; see text).

(up to 420 ppm). Further, within the first group, C2
and Li2 Cþ 2 with kDgl of about 2 900 ppm can be
differentiated from MC2 having a smaller kDgl of
about 2 400 ppm on average. As discussed next, these
trends can be rationalized on the basis of symmetry
arguments.
As pointed out by the q and SD data (Table 1), both
C atoms in Li2 Cþ2 ðD2h Þ and bent MC2(C2v) have very
similar SD distribution as in C2 2 ðD1h Þ: Further, the
presence of an homonuclear C2 2 unit in these
2 polyatomics is dictated by the existence of a reflection
plane perpendicular to the CC bond.
þ
For C2 2 and Li2 C2 having inversion centers, the
selection rule g $ g applies. For the anion, X2 Sþ
g ð2sg Þ
couples magnetically with 2 Pg (1pg ), which
contributes negatively to Dg’ (excitation SOMO !
virtual MO (VMO)). This coupling mechanism is
essentially maintained in Li2 Cþ 2 þ
2 ; where X Sg ð2sg Þ
2 2
2
and Pg(1pg) of C2 correlate with X Ag(2ag) and
2
B3g(1b3g)/2B1g(1b1g) of the cation, respectively.
 P.J. Bruna, F. Grein / Journal of Molecular Structure (Theochem) 617 (2002) 149–168 165

Table 13
Main excited states contributing to the Dg-shifts in various symmetry point groups

Point group Excitation from Dgxx( ’ o) Dgyy(k)a Dgzz( ’ i)

SOMO(py 2 py) ! VMO(· · ·)b (pz 2 pz) (px 2 px)

D1h X2 Sþ
g ! ð2sg !Þ 12Pg(1pgz) 2
S2g 12Pg(1pgx)
D2h X2 Ag ! ð2ag !Þ 13B3g(1b3g) 2
B2g 12B1g(1b1g)
C2v X2 A1 ! ð3a1 !Þ 22B2(2b2) [12B2(1b2 ! 3a1)]c [1 B1(1b1 ! 3a1)]d
2
12A2(1a2)
C1v X2 Sþ ! ð3s!Þ 22P(2pz) [12P(1pz ! 3s)]d 2 2
S 22P(2px) [12P(1px ! 3s)]d
a
D1h, D2h and C1v: upper states generated by double-excitations (no contribution to Dgyy).
b
VMO stands for virtual MO. This excitation contributes negatively to Dgxx and Dgzz.
c
Excitation: occupied MO ! SOMO; contributes positively to Dg-component as 1b2 acquires some pg character [8,9].
d
Excitation: occupied MO ! SOMO (p ! s); contributes positively to Dg-component.

Since SO, L and DE for the two D2h excited states are
quite alike (Table 8), their negative contributions to
Dgxx( ’ o) and Dgzz( ’ i) of Li2 Cþ 2 are not only of
similar magnitude to each other but also to that of C2
2 :
In both radicals, there are no virtual MOs of the
appropriate symmetry to give 2nd-order contributions
to Dgyy(Dgk), a shift thus governed by 1st-order terms
(GS expectation values).
Summing up, the inversion-symmetry radicals C2 2 exist two other 2nd-order magnetic couplings which
and Li2 Cþ2 undergo equivalent magnetic couplings
sg $ pg ; resulting in negative kDgls of a similar
magnitude.
For bent MC2(C2v), the 1pg MO of C2 2 correlates
with 2b2(pz 2 pz) and 1a2(px 2 px), and accordingly,
the coupling of X2A1 with 22B2(3a1 ! 2b2) and
12A2(3a1 ! 1a2) should contribute negatively to
Dgxx( ’ o) and Dgzz( ’ i) of MC2, respectively.
In the lower C2v symmetry, however, there also
contribute positively (occupied MO ! SOMO

Table 14
Calculated g-factor components and comparison with available experimental results

Radical gxx gyy gzz kgl

C2H X2Sþ 2.00274 2.00216 2.00274 2.00255

Expt. Ar [1] 2.0025 2.0025 2.0025(5) 2.0025(5)
Ar [3] 2.00288 [2.002319] 2.00288 2.00269(5)
Kr [3] 2.00143 2.00239(5) 2.00143(5) 2.00175(5)
Curla 2.00303 2.00303 2.00279b
C2
2 X2 S þ
g 2.00115 2.00216 2.00115 2.00149
Curlc 2.00110 2.00110 2.00151b
Li2 Cþ
2 X2Ag 2.00085 2.00211 2.00103 2.00133
LiC2 X2A1 2.00160 2.00322 2.00120 2.00201
12B1 2.00233 2.01150 2.00337 2.00573
X2Sþ 2.00482 2.00216 2.00482 2.00393
Expt. Ar [2]d 2.0021(6) 2.0135(40) 2.0030(6) 2.0062
NaC2 X2A1 2.00143 2.00339 2.00126 2.00203
12B1 1.99700 2.01267 2.00341 2.00595
Expt. Ar [2]d 2.0015(6) 2.0124(30) 2.0036(6) 2.0058
BeCþ
2 X2A1 2.00148 2.00240 2.00109 2.00166
X2Sþ 2.00241 2.00215 2.00241 2.00232
MgCþ
2 X2A1 2.00194 2.00286 2.00116 2.00199

The y-axis is collinear with the C–C bond; C2v and D2h radicals lie on the yz plane.
a
Using Curl equation, and experimental g [6,7].
b
Assuming gyy ¼ ge :
c
Using Curl equation, and experimental g [10].
d
Original gyy and gzz assignment exchanged by us.
166 P.J. Bruna, F. Grein / Journal of Molecular Structure (Theochem) 617 (2002) 149–168
excitations). These two new contributions (when
þ
compared with C2 2 and Li2 C2 ) result from the
absence of inversion symmetry, or equivalently, by
the lifting of the g/u restriction. In fact, mixing
between sg (a 1)/pu (a 1,b 1) and between su (b2)/
pg(a2,b2) becomes allowed (via their in-plane com-
ponents a1 and b2, respectively).
In detail, the 3a1 SOMO of bent MC2, besides its
sg-type composition (py 2 py)/(s 2 s), also acquires
some pu character (pz þ pz). Hence, the excited state
12B1(1b1 ! 3a1)—nominally related to a pu ! sg
excitation forbidden in higher symmetry—couples
positively with X2A1, via the overlap between
(px þ px)[b1] and the (pz þ pz) portion contributing
to 3a1. As seen in Table 10, the L values are
accordingly not too large (< 0.3 a.u.), but since
DE(12B1) is low (< 1 eV), the contributions to Dgyy
are comparatively substantial (from 540 to 1080 ppm
for most compounds, with the exception of BeCþ 2 This work complements our previous study on the Dgs
(< 80 ppm)).
Another positive contribution in bent MC2—now
for its Dgxx component—relates to the coupling with
12B2(1b2 ! 3a1), which in C2 2 corresponds to a
forbidden magnetic transition of type 1su ! 2sg
[(s 2 s) ! (py 2 py)/(s þ s)]. In C2v, the 1b2(1su)
MO gets some admixture of pg(pz 2 pz), which in
turn can overlap with (py 2 py) of 3a1 (SOMO). This
positive contribution is not too large for LiC2, MgC2
and NaC2 (90 –230 ppm) because of the relatively high
DE and poor L (Table 10). (For BeCþ 2 ; it contributes
negatively by about 2 50 ppm.) On the other hand, the
negative coupling with 22B2(3a1 ! 2b2), a state
correlating with 2Pg(1pg) of C2 2 ; is of a larger
magnitude than the positive one due to 12B2 (Table 10).
In short, for C2v radicals it holds that: (1) Dgzz is
negative, and of similar magnitude as for C2 2 and
Li2 Cþ2 (the SOMO of the coupled upper state retains
its (px 2 px) character throughout); (2) Dgxx is also
negative but not as large as Dgzz (due to a small
positive contribution compensating for the negative
coupling 3a1 $ 2b2 ðsg $ pg Þ); and (3) Dgyy is
moderately large but positive, an interaction unique
to the Dgk(CC) component in bent MC2. Thus, the
corresponding kDgls are still negative but not as large
as for the radicals with an inversion center (2 400 vs
2 900 ppm).
The positive kDgls in the linear CCX (C1v)
systems arise, more or less, from the successive loss
of symmetry restraints upon the CC bond in passing
from D1h/D2h to C2v to C1v: in the linear systems,
both the positive DOMO ! SOMO (1p ! 3s) and
the negative SOMO ! VMO (3s ! 2p) are allowed.
However, the former coupling dominates over the
latter, mostly due the low energy of 12P but the high
one of 22P.
It should be noted that positive contributions of
type p ! s only affect Dgk of bent MC2 and Dg’ of
linear CCX.
5. Summary and concluding remarks
The hfccs and g-shifts have been studied theoreti-
cally for a family of isovalent C2 2 -containing radicals,
þ þ þ
namely C2 2 ; Li C
2 2 ; bent LiC 2 NaC2, BeC2 ; MgC2 ;
,
linear CCH, CCLi, CCBe , and skewed HCCLiþ.
þ
for C2 2 and bent LiC2, NaC2 by reporting the
corresponding hfccs. To the best of our knowledge,
nothing has been reported in the literature for the
remaining radicals, except CCH.
The main objective of this investigation was to
predict reliable ESR data for the C2 2 -unit in different
environments (i.e. compounds), and to establish
definitely (via the hfccs) whether the ESR spectra
attributed by GDW to the C2v radicals Liþ C2 þ 2
2 ; Na C2
actually correspond to these species or not. Pre-
viously, we calculated the kDgls for the GSs to be
negative and small (like C2 2 ), whereas, according to
experiments, they are positive and large.
The correctness of our findings about kDgl of C2 2
(MC2) is supported by two experimental features: (i)
other 9VE diatomics, such as BeF, BO, COþ, CN,
Nþ2 ; all have negative kDgls [14], suggesting that kDgl
of C2 2 should be negative, too; and (ii) the g constant
of gas-phase C2 2 was found to be positive, and
therefore, according to Curl’s equation, Dg’ has to be
negative. Since Dgk is small, kDgl should be negative
as well.
The hfccs presented here confirm that the carriers
of the ESR spectra were not bent Liþ C2 þ 2
2 ; Na C2 ;
since the theoretical Aiso(C)s for the GSs are only
25% of the (estimated) experimental values. Simi-
larly small Aiso(C)s lying below 100 MHz have been
reported experimentally for C2(a3Pu) and Cþ 4 2
2 ðX Sg Þ:
Such a consistency between theoretical ðC2 2 Þ
 P.J. Bruna, F. Grein / Journal of Molecular Structure (Theochem) 617 (2002) 149–168
and experimental (C2, Cþ 2 ) values of the isotropic
term is understandable since all these systems have
in common a 2sg(py 2 py) SOMO with little (s þ s)
contribution.
For LiC2 and NaC2 in their 12B1 (p-type) states,
the Aiso(C)s are even smaller than for the GS, i.e. they
cannot be associated with the ESR spectra either,
despite of the good agreement, even though fortui-
tous, between the experimental and theoretical g-
shifts.
In all radicals studied here, there exists a well
defined C2 2 moiety, which has been known long time
ago to be so for bent LiC2 and NaC2, as the Li, Na atoms
have rather low (s ! 1) ionization potentials. Since
such potential is substantially larger for Beþ, Mgþ, our
originally intention for studying BeCþ þ
2 , MgC2 was to
2
get a C2 unit having a spin-density (charge) distri-
bution more distorted than in Liþ C2 þ 2
2 or Na C2 :
However, several calculated parameters (e.g. Re(CC),
v(CC), Aiso/Adip for C, and rather small Aiso(Mþ))
indicate that the reaction of C2 with Beþ or Mgþ also
results in the almost complete transfer of one (s) Mþ
electron to the diatomic, leading to M2þ C2 2 products.
This feature is in line with C2 having an electron
affinity of < 3.5 eV [48], as high as for the strong
electron-acceptor atoms F and Cl.
The stability of the hf parameters—Aiso(C) in
particular—upon changes in DFT methods and basis
sets was also investigated. In that regard, the CCH
results are used as standards, since this is the only
radical among the present ones for which reliable
experimental hfccs are available, therefore serving as
benchmark about the accuracy expected for others.
Very reassuringly, Aiso(C) of CCH changes
relatively little with the DFT approach (albeit only
four DFT methods were considered) and most
significantly, with the basis sets as well. For instance,
Aiso(C)s calculated with B3LYP/6-311þ þ G
(2df,2pd) differ by a few MHz from the B3LYP/
aug-cc-pVQZ results; both reproduce well the exper-
imental values.
Except for the linear CCX radicals, for which there
are 15 –30% s-contributions, the SOMOs of other
radicals are mainly of p(C)-character, as pointed out
by theoretical Adip(C) values being essentially one-
half the value assigned to Adip(2p) of the C atom.
Summing up, the identity of the species detected by
GDW via ESR remains unclear. Our calculations on
167
þ
Li2 Cþ
2 and HCCLi (radicals which besides LiC2
could also have been formed hypothetically in the
photolysis of C2H2 þ Li, as done by GWD), similarly
discard both cations as carriers since their Aiso(C)s are
much smaller than the experimental values.
At this point, it is worth mentioning that, according
to experimental [49,50] and theoretical [51] studies,
the (C2v) radicals C2H2M (M ¼ Li, Na, K) have
Aiso(C) values ranging from 195 to 242 MHz. As well,
the experimental kDgl of C2H2Li was found to be
positive (< 600 ppm), a feature in line with a p-type
SOMO having a main pg(pz 2 pz) contribution from
C2, plus py(Li). Certainly, these ESR parameters are,
to a certain extent, in closer agreement with those
(erroneously) assigned by GDW to bent LiC2, NaC2
(< 233 MHz and positive kDgl, about 3700 ppm) than
the values calculated here for both s-type systems
MC2 (Aiso(C) , 100 MHz, and negative kDgl, about
2 300 ppm).
Acknowledgments
This paper is dedicated to Prof. William Meath on
the occasion of his 65th birthday. The authors thank
NSERC (Canada) for financial support.
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