Semiclassical treatment of electronic transitions in molecular collisions: Three-dimensional H+ + D2 → HD+ + D

✍ Scribed by Ying-Wei Lin; Thomas F. George; Keiji Morokuma

• Publisher: Elsevier Science
• Year: 1975
• Tongue: English
• Weight: 615 KB
• Volume: 30
• Category: Article
• ISSN: 0009-2614
• DOI: 10.1016/0009-2614(75)85495-9

✦ Synopsis

A semiclassical study is carried out for the threedimensional reaction H" + Dz -HD* + D, which invo:vcs an electronic transition from the pound to the first excited singlet state of the Hi system. The potential energ surfaces corresponding to the two singlet states exhibit an avoided intersection, and they arc annalytically continued into the complex nuclear coordinate plane. S-mntris elements in the classical limit are computed from complex-valued classical trajectories which propagate on the analytically continued surfaces and switch surfaces continuously at the complex intersection. These elements are computed for the transition from the+,sround rotational and vibrational states of Dz to the ground rotational and first exited vibratior.al states of HD. for zero total angular momentum and for energies in the range from 4.0 eV to 5.0 eV relative to the bottom of the Da well on the loa-er surface.