Structure and dissociation energy of the weakly bound complex CH[sub 5][sup +](H[sub 2])
- Univ. of Georgia, Athens, GA (United States)
- Univ. of Georgia, Athens, GA (United States) Universitaet Erlangen-Nuernberg (Germany)
The possible low-lying stationary points of CH[sub 5][sup +](H[sub 2]) have been investigated using high level ab initio quantum mechanical techniques. All structures were optimized up to the TZ2P CISD level of theory. The global minimum structure (1) was also optimized at the TZ2P CCSD(T) and TZ2P+d CCSD levels. Four C[sub s] structures, which have H[sub 2] bound to one of two protons of the three-center-two-electron bond of the CH[sub 5][sup +] subunit, have essentially the same energy. Consequently, several internal degrees of freedom in CH[sub 5][sup +](H[sub 2]) are virtually completely unrestricted. We determined the dissociation energy D[sub 0] of CH[sub 5][sup +](H[sub 2]) to be 1.46 kcal/mol [TZ2P+d CCSD(T)]. Harmonic vibrational frequencies have been evaluated for all structures at the TZ2P SCF level of theory; for the energetically lowest-lying structure (1), we also determined the vibrational frequencies up to the TZ2P CCSD level. The H-H stretching frequency shift ([minus]83 cm[sup [minus]]) predicted theoretically is in excellent agreement with the recently determined experimental value ([minus]83.6 cm[sup [minus]1]). The average value of theoretical rotational constants for the energetically lowest lying stationary points (1-4) and one other minimum (7) compares moderately well with the experimental result. 35 refs., 2 figs., 9 tabs.
- DOE Contract Number:
- FG09-87ER13811
- OSTI ID:
- 5525680
- Journal Information:
- Journal of Physical Chemistry; (United States), Vol. 97:47; ISSN 0022-3654
- Country of Publication:
- United States
- Language:
- English
Similar Records
Is there a potential minimum corresponding to singlet methylnitrene A study of the CH[sub 3]N to CH[sub 2]NH rearrangement on the lowest singlet state potential energy hypersurface
Carbonyl--water hydrogen bonding: The H{sub 2}CO--H{sub 2}O prototype
Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS
COMPLEXES
DISSOCIATION ENERGY
MOLECULAR STRUCTURE
QUANTUM MECHANICS
REACTION INTERMEDIATES
THEORETICAL DATA
VIBRATIONAL STATES
DATA
ENERGY
ENERGY LEVELS
EXCITED STATES
INFORMATION
MECHANICS
NUMERICAL DATA
400201* - Chemical & Physicochemical Properties
661100 - Classical & Quantum Mechanics- (1992-)