화학공학소재연구정보센터
Journal of Chemical Physics, Vol.103, No.7, 2548-2554, 1995
6D Quantum Calculation of Energy-Levels for HF Stretching Excited (HF)(2)
Converged full-dimensional (6D) quantum mechanical calculation of energy levels of intramolecular stretching excited (HF)(2)(v(1)v(2)) is presented for (v(1)v(2))=(01), (10), (02), (20), and (11). The bound state calculation for the excited HF dimer employs the SQSBDE potential energy surface of Quack and Suhm and is for total angular momentum J=0. This calculation provides the first rigorous theoretical result of energy levels for HF stretching excited HF dimer in full dimensions. The calculated fundamental transition frequencies are v(1)=3940.6 cm(-1) and v(2)=3896.4 cm(-1). These values are somewhat larger than the corresponding experimental measurement of 3930.9 cm(-1) for v(1) and 3868.3 cm(-1) for v(2). The overtone frequencies are calculated to be 2v(1)=7713.5 cm(-1), 2v(2)=7642.5 cm(-1), and v(1) + v(2)=7841.8 cm(-1). The theoretical tunneling splittings of the fundamentals v(2) and v(1) are, respectively, a factor of 5.3 and 3.7 smaller than the ground state splitting, compared to a factor of 3 from the experimental measurement. The splittings of the overtone states 2v(2), 2v(1), and v(1) + v(2) are smaller than that of the ground state by factors of 9.6, 48, and 1.8, respectively. Some of the calculated energy levels of excited (HF)(2) are spectroscopically characterized and assigned.