科研之友
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摘要
A highly correlated approach using curvilinear valence coordinates is applied to calculate the vibrational fundamentals and some combination modes of the formamide molecule with high accuracy. A series of potential energy surfaces (PESs) has been generated by AGAPES, a program for adaptive generation of adiabatic PESs, at various electronic structure qualities until excellent nonaccidental agreement with the experimentally assigned fundamental transitions was reached at the CCSDT(T)-F12a/aug-cc-pVTZ level of theory using the improved relaxation method of the Heidelberg multiconfiguration time-dependent Hartree (MCTDH) package in connection with an exact expression for the kinetic energy in valence coordinates generated by the TANA program. By comparison of the overtone series nu(1)-3 nu(1) to experiment, we demonstrate that the known problems concerning the floppy vi wagging motion are solved within this approach. The potential energy coupling as well as the vibrational coupling in curvilinear coordinates is discussed together with the efficiency of this approach.
- 出版日期2015-12-3
