Jml. Martin et Pr. Taylor, AB-INITIO STUDY OF THE ISOELECTRONIC MOLECULES BCN, BNC, AND C-3 INCLUDING ANHARMONICITY, Journal of physical chemistry, 98(24), 1994, pp. 6105-6109
The ground states of BNC, BCN, and C-3 were studied using the full-val
ence CASSCF (complete active space SCF) and CCSD(T) (augmented coupled
cluster) methods and basis sets of spdf and spdfg quality. Full quart
ic force fields were obtained. r(c), and stretching fundamentals for C
-3 are found to be in excellent agreement with experiment; r(0) and th
e bending fundamental reveal shortcomings in the bending part of the p
otential. The BNC ground state ((1) Sigma(+)) is only slightly less st
rongly bound than C-3 and is 9.5+/-0.5 kcal/mol lower in energy than t
he ground state of BCN. No other low-lying structures or states were f
ound. Stretching fundamentals in BNC are affected by a severe Fermi re
sonance. Best estimates for the molecular constants are as follows. BN
C: Sigma D-0 = 300.5+/-1 kcal/mol, r(c)(CN) = 1.167 Angstrom, r(c)(NC)
= 1.416 Angstrom, omega(1) = 2075 cm(-1), omega(2) = 998 cm(-1), omeg
a(3) = 131 cm(-1), v(1) = 2076 cm(-1), v(2) = 991 cm(-1). BCN: Sigma D
-0 = 291.0+/-1 kcal/mol, r(c)(CN) = 1.135 Angstrom, r(c)(BC) = 1.597 A
ngstrom, omega(1) = 2197 cm(-1), omega(2) = 812 cm(-1), omega(3) = 204
cm(-1), v(1) = 2166 cm(-1), v(1) = 810 cm(-1). Both stretching fundam
entals are computed to have high infrared intensities for both BNC and
BCN. Spectroscopic constants for isotopic forms are also given. The b
est computed Sigma D-0 for C-3 is 314.7+/-1 kcal/mol, in very good agr
eement with experiment but with a smaller uncertainty.