.IOVRNALOF MOLECuL.

aR
SPECTROSCOPY
39, I‘%158 (1971)

Rotational Constants for HCN and DCN

GISBERT WINNEWISSER’

National Research Council, Ofiawa, Canada

AND

ARTHUR G. KHAKI AND DOKALD R. JOHPXOX

A’afional Bttrealc of Standards, Washington, D.C. 20134

Microwave measurements of rotational transitions within vihrat,ionally

excited st,ates of several isotopic species of HCN have given improved values
for the pertinent B, constant’s. These new dat’a have been combined with
infrared measurements given in the literature (including D, terms) to arrive at
a set of rovibrational constants (CXand y constants) which is consistent with
all available data. Bond distances resulting from several different B, approxi-
mations are intercompared to assess the variability of the rc values and the
importance of the 7 terms. The latest ~0 and T, bond distances are also given.

INTKODUCTIOK
A large amount, of infrared data is now available on various vibrational states
of HCY and DCN ; but, because of the inconvenient’ly high frequencies of the
lowest AJ = 1 transit’ions, microwave measurements have only been reported
for the ground vibrat’ional st#at,e.We have now measured rotational transit,ions
in some of t’he lower vibrational states of several isotopic species of HCN.
These new measurements have been combined with existing infrared measure-
ments t’o obt’ain a complete set of rotational constants (o( and y terms) for both
HCN and DCN. Those con&ants malre it possible to calculate term values with
a high degree of confidence. Since the y t’ermx may be more important for the
HCK molecule than for most other polyatomic molecules, we have investi-
ga,ted their importance for the calculation of rs st,ructures and it is found that
they may be ignored wi-ithout’ significantly affecting the bond distance calcula-
tion.

NEW MICROWAVE MEASUREMEKTS

The microwave measurements were made on spectrometers at the Nat,ional
Bureau of St’andards (USA) and t.he National Research Council of Canada.

1Present address: Department’ of Physics, University of British Columbia, Vancouver,

B.C., Canada.
119
 TABLE I
NEW MICROWAVE MEASUREMENTS
- -
J’c J”
juadrupole’ J’t J”
Vib. Quadrupoleb
Molccult Frcq. (MHz)” k?b. State F’ c F” Molecule Freq. (MHz)~
State F’ c F”
__- .-
HCN 178138.37 zt 0.15 2+l Ol’dO ItO HCN 89090.13 f 0.15 1+-o 0200 O+l
HCN 89087.92 f 0.10 1+--o 0200 2+1 2
HCN 178136.76 f 0.10 2+-l Ol’dO

HCN 178135.25 f 0.15 2+1 Ol’dO 2+-l HCN 89086.53 f 0.15 l+O 0200 1+-l
2
HCN 177240.65 f 0.15 2+1 ol’co l-0 HCN 88027.20 f 0.20 I+0 lO%l unresolved ;
3 + 21 HWN 86342.16 f 0.10 ItO 0000 0+-l
HCN 177238.96 f 0.10 2+-l Ol’CO
1 +- l( HWN 86340.05 f 0.10 ItO OD”0 2tl K!
HCN 177237.45 f 0.15 2+1 01’CO 2+1 HWN 86338.75 f 0.10 I+0 0000 1-l “P
HCPN 86055.05 f 0.10 1+-o 0000
DCN 145891.42 f 0.10 2tl 0200
DCN 72950.57 f 0.10 1+-O 0203 O-1 E
DCN 72948.48 f 0.10 It0 0205 2+-l Y
DCN 145889.98 f 0.15 2+-l 0200
DCN 72947.16 f 0.10 1+-o 0208 1+-l
145720!07G + 0 .lQ OlldO $
UCN I+1 l+Q UCN 72022.00 zt 0.20 1+-O 1000 unresolved u
13 + 21 DWN 71667.6 f 0.4 l+O 02@0 unresolved
UCN 145719.28 f 0.10 2+-l Ol’dO
D WN 71177.36 f 0.10 l+O 0000 O+l z
11 + 11
DCN 145717.85 f 0.15 2cl Ol’dO 2+1 D’SCN 71175.22 f 0.10 1+-O 0000 2-l g
DCN 144976.17 f 0.10 2+1 ol’ro ItO IPCN 71173.89 f 0.10 It0 0000 l-1
13 + 21 DCYN 70853.95 f 0.30 l+O 0200
DCN 144974.64 f 0.10 2+1 Ol’CO
11 +- 11
DCN 144973.18 f 0.15 2+-l Ol’CO 2+1 DCY5N 70339.48 f 0.10 It0 0000
_ -
* The uncertainties indicate a liberal d~(JW~IJCe for calibration and measurement errors but do not, incltrde errors due t,o failure
to resolve hyperfine structure.
h The deuterium quadrupole split,ting was too small to observe.
 ROTATIONAL CONSTANTS FOR HCN AND DCN 151

The NBS measurements utilized Stark modulation techniques while the KRC
measurements employed source modulation. Some measurement’s were made in-
dependent,ly at both laborat’ories and were subsequent,ly found to be in agree-
ment, to within the quoted error limit’s. The observed transitions are given in
Table I.
The 3, values derived from the microwave measurements are given in Table
II. The constant)s given by De Lucia and Gordy (f ) were used t,o correct for the
hyperfine splitting although it. was necessary to ignore the quadrupole splitting
(about 0.1 MHz) due to deuterium since we could not resolve the individual
component,s.
The correction for centrifugal dist’ortion was made using D, values defined by
D, = D, + &(R) + C&(Q) + &(~x), (1)
where Do was given the value measured by De Lucia and Gordy (I), and t.he
vibrationally dependent terms were determined from infrared measurements
(see section on rot.ation-vibration constants). For t.he carbon-13 and nitrogen-15
isotopic species we assumed that the isotopic shift, in D was the same as that
calculated by Nakagawa and Merino (2). It is estimated t,hat# the errors in the
centrifugal distortion corrections make insignificant contributions t,o the errors
in the R values.
TABLE II
ROTATIONALCONSTANTSGIVEN BY MICROWAVE MEASUREMENTS FOR VARIOUS
HCN SPECIES

Molecule Vibrational State B, (MHz)* D, @Hz) --

-
HCN 0000 44 315.9755 i O.OOM’~, r 87.22”. c
HCN 01’0 44 422.444 xt 0.03’: 89.4e
HCN 0200 44 544.04 f 0.06” 91.6e
HCN 1000 44 013.77 & O.l@ 86.9
H’YX 0000 43 170.08 z!z 0.06” 83.0d
HCPN OODO 43 027.69 +z 0.05’ 82.3d
DCN 0000 36 207.4627 f 0.0002’~ 57.83h
DCN 01’0 36 337.043 f 0.03” 61.1e
DCN 0200 36 474.25: f 0.036 64.3e
DCN 1000 3B 011.11 f O.l@ 57.48
D’“CN 0000 35 587.62 f 0.05e 55.7d
D’“CN 0200 35 833.9 i 0.28 59.5*
DC’jN 0000 35 169.85 zt 0.05’ 54.P
DC’5N 0200 35 427.09 f 0.15’ 58.-P

s The uncertainties indicate a reasonable allowance for calibration and measurement

errors but do not include errors due to failure to resolve hyperfine structure.
b F. De LCCIA and W. GORDY, Phys. Rev. 187, 58 (1969).
c A. G. MAKI, W. B. OLSOE;, and R. L. SAMS, J. Mol. Spectrosc., 36, 433 (1970).
d T. XAKA~AWA and Y. MORINO, J. Mol. Spectrosc. 31, 208 (1969).
c This work.
152 WINNEWISSER, MAKI, AND JOHNSON

TABLE III
ROVIBRATIONAL
CONSTANTS(B’-B”) FOR DCN. ALL VALUESARE GIVEN
IN WAVENUMBERS (cm-i) X 105

Transition Observed% Transition Observed” ~$~- Ref.

! I

10~&00~0 -655.3 f 2.4 -655.8 b 0221-0220 -969.9 f 2.1 -968.0 b

20%-0000 -1363. f 15. -1363.0 c 11’0-00~0 -243.2 f 4.0 -243.0 b
00~1~0000 -1032.9 & 1.5 -1035.0 b 11’0-01’0 -671. f 12. -675.2 b
0001-01’0 -1472. & 12. -1467.3 b 12~0-01’0 -241.4 f 2.4 -237.0 b
OOYXKYO -2069.5 zt 3.0 -2069.8 b 12+01’0 -276.8 z!z 4.8 -273.2 b
01’0-00~0 434. f 15. 432.3 b 10~1-00~0 -1661.0 f 1.0 -1659.5 b, d
01’1loO~0 -567.1 f 3.3 -569.3 b 11’1-01’0 -1639.6 & 1.8 -1645.5 b, d
Ol’lXll’O -1003.4 zt 2.7 -1001.5 b 0220-02~0 -35.8 f 0.5 -36.2 e
01’2-01’0 -2013. f 18. -2002.8 b 0330-03~0 -72.9 f 0.9 -72.3 e
02~1-02~0 -969.9 f 2.1 -968.0 b

a1 = 600.5 f11.4’ Y13 = 31.2 f 1.8

oz.. = -423.3 f 1.0 yzz = 3.65 & 0.19
cy3 = 1084.4 f6.5 Y23 = 33.5 f 1.0
“If11 = -25.7 f 5.5 Y33 = 0.1 zt 2.1
Y12 = -19.4 Al.1 721 = -9.04 f 0.09

8 The uncertainty in the B’-B” values is three times the standard deviation estimated
from a least-squares analysis of the infrared data except where the measurements were not
available.
b A. G. MAKI, E. K. PLYLER,and R. THIBAULT,J. Opt. Sot. Amer. 64, 869 (1964).
c H. C. ALLEN,JR., E. D. TIDWELL,and E. K. PLYLER, J. Chem. Phys. 26, 302 (1956).
d D. H. RANK, G. SKORINKO, D. P. EASTMAN,and T. A. WIGGINS,J. Opt. Sot. Smer.
60, 421 (1960).
e From microwave measurements; see Ref. (3).
f The uncertainty in the (Yand y constants is the estimated standard deviation of these
constants; see text for comment on the correlation of the constants.

It may be noted that the J = 2 t 1 transitions of the 02’0 st,ate of DCN are
about 3.68 MHz lower than predicted from the J = 1 +- 0 transit’ion. This
discrepancy is due to the effect of l-type resonance which affects the J = 2
level of the 02”O state but not the J = 0 or 1 levels. Using equations and con-
stants given by Maki and Lide (S), it is predicted that’ the transibion should be
lower by 3.60 MHz in excellent agreement with experiment’.

EVALUATION OF THE ROTATION-VIBRATION CONSTANTS

The rotation-vibration constants were evaluated by combining in a least
squares fit the microwave measuremenus given above and all available infrared
information. Since infrared measurement’s give more accurate values for B,’ - 8,”
than for either B, , the fit was made using such AB values. Table III lists all the
 133
ROTATIO?;AL CONSTANTS FOR HCN AND DC3

Table IV

RovibrationalConstants (B'-B")for HCN. All Values are Given in Wavenumbers(~m-~)%lO~.

Transition Observeda Calculated Ref. Transition Observed= Calculated Ref.

lo"O-OO"0 -1007.2-2.4 -1007.1 b 13~0-0200 -671.2 13.6 -672.8 c

20~0-00~0 -2019. -16. -2021.2 c 13"0-02*0 -757. 110. -753.6

00~1-00~0 -1042.1~0.9 -1042.3 d 21~0-00‘0 -1691. 230. -1694.
00'1-01'0 -1399.OiZ.l -1397.5 e Ol'l-OO"0 -665.9-6.0 -665.7
oo-2-ooco -2114.9i0.9 -2114.9 f 0251-01'0 -592.6i4.8 -593.7 r,k
00:3-00"0 -3213.4r9. -3217.6 g 02'1-0110 -676.7 -1.8 -674.5 e,k
00 4-00‘0, h 02?1-02co -998.9+1.5 -999.4
-9376. ill. -9375. g
30'2-OO"0. 0221-02~0 -998.9 -1.5 -999.4
00'5-00~0 -5523. !30. -5514. g 01'2-01'0 -eo70.5!3.0 -2072.0 k
00;6-OO"0 -6722. !30. -6707. g 01'3-01'0 -3154.2~9.6 -3153.2 g
Ol'O-OO"0 354.6-9.0 355.14 c
lO"l-00'0 -2028.6'3.0 -2027.4
02~0-00~0 759.815.7 760.91 e,i
10'2-00'0 -3076.2L8.7 -3077.8
03'0-00~0 1135.6:3:0 1136.5 b
10~3-00:0 -4158.4
-4159.8'8.4
04'0-00'0 1563.6r1.2 1562.7 c -5106.
20'3-00'0 -5112. J27.
04:0-01'0 1213. 412. 1207.5 b
loos-0020 -6410.
-6405. i18.
04:'0-01'0 1116. i15. 1126.7 b
11'1-00'0 -1664.5
-1663.5-3.0
05'0-01'0 1590. i15. 1603.5 c
-2682. i24. -2693.
11'2-oo;o
11'0-00~0 -665.0i0.6 -665.7 c
1202-OO"0 -2259.
-2273. .24.
11'0-01'0 -1022. 16. -1020.9 b
11'3-01'0 -4104. -21. -4108.
wo-OO"0 -274.8i6.6 -273.7 e 40"2_00'?0'
12',0-0110 -629.2kO.7 -628.8 c loc4-oo"o:
-11274. i30.h -11277. 8
12 0-01'0 -7lO.OiO.9 -709.7 c 02~0-02~0 80.72-10.30 -80.81 b

= 997.5 +1.9p = 22.1 '0.7

?l “13
= -356.16~0.25 ‘/22= 5.11'0.05
?2
= 1044.6 ho.9 v23 = 21.46 0.25
Y3
-3.5 il.0 = -15.10'0.026
Vll = '(33
'112= -13.73i0.25 = -20.20-0.035
yII

(a) The uncertaintyin the B'-B" values is three times the standarddeviationestimatedfrom a least-
squaresanalysisof the infrareddata exceptwhere the measurementswere not available.
(b) See ref. 3.
(c) A. G. Maki, W. B. Olson, and R. L. Sams, J. Mol. Spectrasc.(in press).
(d) D. H. Rank, D. P. Eastman,B. S. Rae, and T. A. Wiggins,J. Opt. Sot. Am. Sl_,929 (1961).
(e) A. G. Maki and L. R. Blaine, J. Mol. Spectrosc.II, 45 (1964).
(f) D. H. Rank, A. H. Guenther,J. N. Shearer,and T. A. Wiggins,J. Opt. Sot. Am. 47, 148 (1957).
(g) See ref. 4.
(h) Sum of AB values for the two transitions.
(i) W. W. Brim, J. M. Hoffman,H. H. Nielsen,and K. N. Raa, J. Opt. Sot. Am. 50, 1208 (1960).
(j) H. C. Allen, Jr., E. D. Tidwell,and E. K. Plyler, J. Chem. Phys. 2, 302 (1956).
(k) D. H. Rank, G. Skorinko,D. P. Eastman,and T. A. Wiggins,J. Opt. Sot. Am. 50, 421 (1960).
(1) A. G. Maki, E. K. Plyler, and R. Thibault,J. Opt. Sac. Am. 2, 869 (1964).
(m) D. H. Rank, R. P. Ruth, and K. L. Van der Sluis, J. Opt. Sac. Am. c, 693 (1952).
(n) D. H. Rank, T. A. Wiggins,A. H. Guenther,and J. N. Shearer,J. Opt. Sot. Am. 46, 953 (1956).
(p) The uncertaintyin the i and ',constantsis the estimatedstandarddeviationof these constants;
see text for crxmnent
on the correlationof the constants.
154 WINNEWISSER, MAKI AND JOHNSON

TABLE V
CENTRIFUGAL DISTORTION DATA& USED TO CALCULATE THE CONSTANTS GIVEN
IN TABLE VI

(D’ - D”) x 106

Transition Ref.
Calcd Exptl

DCN 10%00~0 -0.014 -0.005 f 0.005 b

11’0-01’0 -0.014 0.05 f 0.04 b
00%O1’0 -0.125 -0.15 f 0.06 b
11’0~~0 0.094 +0.093 f 0.012 b
01’1-01’0 -0.017 -0.013 & 0.008 b
00~1-00~0 -0.017 -0.014 f 0.003 b
10~1-0000 -0.031 -0.035 f 0.003 c

HCN 01’0-00~0 0.074 0.068 f 0.007 d

02Y&O0~0 0.148 0.110 f 0.020 e
03%-00~0 0.221 0.220 f 0.020 d
04%00~0 0.295 0.296 f 0.024 f
04%-01’0 0.221 0.36 f 0.08 d
0420-01’0 0.221 0.11 f 0.08 d
10%-0000 -0.009 0.01 f 0.01 d
11’0-00~0 0.065 0.070 f 0.005 f
12%01’0 0.065 0.045 f 0.008 f
12+01’0 0.065 0.065 f 0.009 f
00~1-00~0 -0.027 -0.024 f 0.020 g

01~00
11’1-00~0 0.047
0.037 0.041
0.00 f* 0.020
0.08 :
11’1-00~0 0.037 0.12 f 0.08 h
00’2-00~0 -0.054 -0.05 f 0.02 i
-
* All values given in wavenumbers (cm-l).
b A. G. M.aI, E. IX. PLYLER, and R. THIBAULT, J. Opt. Sot. Amer. 64,869 (1964).
0 D. H. RANK, G. SKORINKO, D. P. EASTMAN, and T. A. WIGGINS, J. Opt. Sot. Amer. 60,
421 (1960).
d Ref. (8).
e A. G. MAKI and L. R. BLAINE, J. Mol. Spectrosc. 12, 45 (1964).
f A. G. MAKI, WM. B. OLSON, and R. L. SAMS, J. Mol. Spectrosc., 36, 433 (1970).
g D. H. RANK, D. P. EASTMAN, B. S. RAO, and T. A. WIGGINS, J. Opt. Sot. Amer. 61,
929 (1961).
h D. H. RANK, T. A. WIGGINS, A. H. GUENTHER, and J. N. SHEARER, J. Opt. Sot. Amer.
46, 953 (1966).
i D. H. RANK, A. H. GUENTHER, J. N. SHEARER, and T. A. WIGGINS, J. Opt. Sot. Amer.
47, 148 (1957).

infrared A& values used in the fit for DCN and Table IV contains a similar
list for HCN. The reported uncertainties represent three times the standard
deviation obtained from the infrared band analyses. The con&ants indicated
in Tables III and IV were defined by t’he equation
 ROTATIONAL CONSTANTS FOR HCN AND IXN 1%

In using Tables III and IV one must be cautioned that, because there is a
high correlat’ion among the CYand y constants, it is necessary to utilize the cor-
relation coefficients (or more properly the variance covariance matrix) to
estimate the uncertainty in any calculated 3, or R, value. Upon request, t.he
authors will send the variance covariance matrix to any interested party.
In the least-squares fit each datum was weighted according to the reciprocal
of the square of the estimated uncertaint,y. It was necessary to go back to the
original published data in order to arrive at a consistent estimate of the un-
certainties. In many cases it’ was evident that more recent data were significantly
better than older work; consequently, many of the older measurements were
not used. We have also taken the liberty of refitting the dat’a of Douglas and
Sharma (4) using the latest values of Bo and Do so that, although we give credit
to the authors, the AB values we have used are not exactly the same as those
given in their paper. Wherever appropriate, the effect of I-t#ype resonance has
been removed in order to get an accurate AB value. For t#he 10”4-000 and
40”2-000 transitions it was also necessary to t,ake into account the large effec-
tive AD terms which resulted from t,he Fermi resonance between 10’4 and 40”2.
Since the resonance mixes the two levels, only t,he sum of the DwoAB values was
used. The resonance also gives a significant perturbation to the OO”4and 30”2
levels. Since the B, values for the levels invoIved in the (~1, v3 1v1 f 3, v3 F 2)
resonance are nearly the same, and since the pert’urbation is very small, for all
other measurements the effect of resonance is smaller hhan the experimental
error.
For both HCN and DCN the agreement between calculated and observed
AB values is consist’ent with the estimated standard errors obtained from the
individual least-squares fits. This is not surprising for DCN since the number of
B, and AB, values is not# much greater than the number of parameters being

TABLE VI
CENTRIFUGAL DISTORTION COKSTANTS~

HCN DCN
Constantb - --___
Expt1° Calcdd Exptlc Calcdd
-
00 x 106 2.909” f 0.001 2.909 1.929e * 0.001 1.926
(21 x 106 -0.009 f 0.01 0.007 -0.014 I!= 0.02 -0.001
dz x 100 0.074 f 0.01 0.071 0.108 f 0.02 0.070
dn x lo6 -0.027 f 0.01 -0.028 -0.017 f 0.02 -0.009
D, x 106 2.853 2.848 1.837 1.861
_____
8 .&II values given in a-avenumbers (cm-‘).
h Constants defined by Eq. (1).
c Experimental values are those determined from the experimental values given in
Table V.
d See Ref. (2).
p See Ref. (I 1.
156 WINNEWISSER, MAKI, AND JOHNSON

determined. For HCN, however, there is sufficient data to indicate that the y
terms have a real significance rather than being correction factors which are
peculiar to only one or two levels.
The centrifugal distortion terms are also necessary for the accurate calcula-
tion of rotation-vibration term values. We have used t,he AD values obtained
from infrared measurement’s given in Table V to determine the vibrational de-
pendence of the distort’ion constants (defined by Eq. (1)). Nakagawa and
Merino (2) have calculated these same constants and Table VI compares t!heir
calculated values wit)h our experiment’al values. It seems likely that experi-
mental error accounts for most of the discrepancy between the calculated and the
observed values.
BOND DISTANCES

Small changes in bond distances from one molecule to another give chemists
information which can be correlated with other changes in t,he chemical bonds.
Spectroscopic measurements lead directly to inverse moments of inertia for
molecules in the ground state, (i.e., Bo) in which the molecule still retains the
zero point vibrational energy. This adds a disturbingly large uncertainty to any
bond dist#ance calculation (unless B, is used), thus obscuring small but significant
differences in the chemical bonds. Costain (5) has proposed the use of substitu-
tion distances (TV)as a means of partially cancelling out the effecbs of zero point
vibration without actually removing it, the idea being that rs distances are more
consistent (have less scatter) regardless of which sets of isotopic species are
used. Laurie and Herschbach (6) suggested that an alternative approach might
be to take into account the fact that the average bond distances (for stretching-
type vibrations) are smaller for heavier atoms because the zero point vibrat’ional
amplitudes are smaller.
In Table VII we give a mat’rix of calculated r. bond distances for all possible
pairs of B. values which have been measured. It can be seen that the use of
H-D pairs gives C-H distances which tre consistently lower than bhe re
distances (givenOin Table VIII) by 0.003 A and C-N distance! consistently
higher by 0.003 A. With H-D pairs a total spread of only 0.0008 A is found for
the C-H distances and 0.0002 8 for the C-N distances. The spread is much
worse if all possible pairs are considered. Some of the other t,rends which are
discernible are :
(a) As pointed out by Laurie and Herschbach the C-D bond distances
calculated using Bo values for pairs of deuterium-containing molecules are
consist,ent,ly smaller by about 0.003 8 from those calculated using &‘s for hy-
drogen-cont’aining species.
(b) The HCN-HC1’N pair of Bo values gives the largest ~0 (C-H)
distances while the D’aCN-DC15N pair gives the smallest ~0 (C-D) dist’ances.
Experimental error contribut’es virtually nothing to the differences in these
extrema.
 ROTATIONAL CONSTANTS FOR HCN AND DCK 157

TABLE VII
INTERATOMICvODISTANCES~IN HCN FOR VARIOUS PAIRS OF R. VALUES

HCN HYN HC’% DCN D”CK

H’%%’ 1.06754 (lO)b

1.15582 (2)
HC’SN 1.07703 (20) 1.06017 (35)
1.15395 (4) 1.15720 (7)
DCN 1.062407 (0) 1.062692 (6) 1.062774 (5)
1.156827 (0) 1.156728 (2) 1,156700 (2)
D’YX 1.062086 (8) 1.062416 (13)1.062496 (14) 1.06585 (9)
1.156889 (2) 1.156780 (4) 1.156754 (4) 1.15564 (3)
DC’6N 1.061930 (8) 1.062256 (13)1.062327 (13) 1.07249 (16) 1.05837 (36)
1.156920 (2) 1.156810 (4) 1.156786 (4) 1.15335 (6) 1.15812 (12)
-~
8 The upper number is the C-H distance in Angstroms and the lower number is the
C=N distance in Angstroms. All calculations used Z = 505376/B(MHz) and unified mass
units given by L. A. K~NIG, J. H. E. MATTAUCH,and A. H. WAPSTRA, Nucl. Phys. 31, 18
(1962).
b The number in parentheses is the uncertainty in the last digit or two due to the uncer-
tainty in the Ba value. This does not take into account the effect of zero-point vibrations
which account for most of the divergence in the various calculations of Q, Note that all
H-D pairs have an extra significant figure.

TABLE VIII
OF DIFFERENT TYPES OF INTERATOMICDIST.ANCES~IN HCN
CO~\IPARISON
-
r(C-H) A r(C-IQ .A r(N-H) .i

r, 1.06316 + O.OOOIOb1.15512 f 0.00015b 2.21828 f 0.00012”

‘rij 1.064 f O.Ollb 1.1564 & 0.0024b 2.2205 f 0.0090b
re (with (Y 1.06549 f 0.00924d 1.15321 f 0.00005d 2.21870 f 0.00020d
and Y)e
re (Rank et aZ.)e 1.06593 f 0.00010 1.15313 + 0.00002 2.21906 f 0.00908
T, (from 100,020,001)’ 1.06573 =t 0.00080d 1.1.5317 f 0.00025d 2.21876 f 0.00060d

a All calculations used Z = 505376/B(MHz) and unified mass units given by L. A. K~NIO,
J. H. E. MATTAUCH, and A. H. WAPSTRA,MucE. Phys. 31, 18 (1962).
b The P, and TOdistances are averages of the values obtained for all possible permuta-
tions of Bu values. The uncertainty is due to the dispersion of the calculated values and
does not allow for measurement errors.
e B,(HCK) = 44512.36 f 0.23 MHz; Z?,(DCN) = 3632!).49f 1.53 MHz.
11The uncertainty is the estimated error limit from the B, values.
c See D. H. Rank, G. SKORINKO, D. P. EASTMAN,and T. A. WIGGINS, J. Opt. Sot. Amer.
60,421 (1960).
f Calculated using B, = 215 Z3o- 16 Bloo - Id B,xo - ?$ R ,,~lfor HCS, DCN, and Dr3CN

(c) Because of the double subst#itution in the pair H’3C’4K-H’2C’5K the

Laurie-Herschbach bond shortening effect should be negligible. Consequently,
the C---S distance calculated for H’3C’4N-H’2C15N should he the same as that
158 WINNEWISSER, MAKI, AND JOHNSON

calculated for the pair D’3C’4N-D12C15N. That is not t,he case and the difference
of nearly 0.001 8 cannot be attributed to experimental error.
(d) For a given measurement error, the uncertainty in the bond distances
for the H’3C’4N-H’2C’5N pair is less than the uncertainty for the HC’4N-HC15N
pair even though the difference in Bo values is ten times greater in the latter pair
(i.e., greater accuracy in bond distance determinations is not assured by taking
Bo values which are farther apart).
If Laurie and Herschbach’s suggestion is followed, it is found that the spread
in T-O values can be significantly reduced by appropriate choices of the bond
shrinkage parameters. This technique is so sensitive to the shrinkage parameter,
however, that its usefulness is in doubt. For the HCN-HC”N pair, for instance,
the assumption that ro(C14N) = ro (C15N) + 0.0001 i rather than ro(C14N) =
~0(C15N) results in diminishing the C-H distance by 0.026 8 and increasing the
C-N distance by 0.005 8.
In Table VIII the various methods of calculating the HCN bond distances are
compared along with the dispersion in the values. It is comforting to note that
the re values obtained using B, values for the 10’0, 02’0, and 007 states to es-
timate B, (last row of Table VIII) are in quite good agreement with the re
values obtained using all a! and y terms to calculate B, (third row of Table VIII).
Rank’s re values are in error by slightly more than he had expected because the
values for a2 were in error by slightly more than was expected.
In conclusion, we find that any systematic way of measuring the cxvalues will
give B, and re values which are acceptable for intercomparing bond distances in
different molecules. For such comparisons the technique of allowing for changes
in bond length as isotopic masses are changed is not yet usable because there is
no good criterion for assigning bond shrinkage parameters, and the resulting
bond lengths are very sensitive to the value of this parameter. The rS distances
still seem to be the most reliable and readily measurable quantities for such
comparisons.

RECEIVED: DECEMBER 7, 1970

REFERENCES

1. F. DE LUCIA AND W. GORDY, Phys. Rev. 187,58 (1969).

8. T. NAKAC+AWAAND Y. MORINO, J. Mol. Spectrosc. 31,208 (1969).
S. A. G. MAKI AND D. R. LIDE, JR., J. Chem. Phys. 47,3206 (1967).
4. A. E. DOUGLAS AND D. SHARMA, J. Chem. Phys. 21,448 (1953).
6. C. C. COSTAIN, J. Chem. Phys. 29, 864 (1958).
6. V. W. LAURIE AND D. R. HERSCHHACH, J. Chem. Phys. 37, 1687 (1962).