Naslov
Ground and asymmetric CO-stretch excited state tunneling splittings in the formic acid dimer

Autori
Matanović, Ivana ; Došlić, Nađa ; Kuehn, Oliver

Izvornik
The Journal of chemical physics (0021-9606) 127 (2007), 1; 014309, 7

Vrsta, podvrsta i kategorija rada
Radovi u časopisima, članak, znanstveni

Ključne riječi
ground state tunneling splitting ; vibrationally excited state ; tunneling splitting ; formic acid dimer ; CO stretch

Sažetak
There has been some controversy concerning the assignment of measured tunneling splittings for the formic acid dimer in the vibrational ground state and the asymmetric CO-stretching excited state. This is related to the question whether the fundamental excitation of the CO-vibration promotes or hinders tunneling. Here we will address this issue on the basis of a five-dimensional reaction space Hamiltonian which includes three large amplitude coordinates as well as two harmonic modes whose linear superposition reproduces the asymmetric CO-vibrational mode in harmonic approximation. Within density functional theory using the B3LYP functional together with a 6-311++G(3df, 3pd) basis set we obtain a ground state tunneling splitting which is about 2.4 larger than the one for the CO-stretching excited state.

Izvorni jezik
Engleski

Znanstvena područja
Kemija

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