Computation of electronic transition moments: the length versus the velocity representation |
| |
Authors: | Charles W Bauschlicher Jr Stephen R Langhoff |
| |
Institution: | (1) NASA Ames Research Center, 94035 Moffett Field, CA, USA |
| |
Abstract: | Summary We have compared transition moments (TMs) obtained using the length and velocity representations for transitions from the ground state of H2 to the lowest two1
u
and two1
u
+
Rydberg states, theA
1 –X
1 + transition in BH, and theA
1
u
–X
1
g
+
transition in C2. For H2, the TMs in the length and velocity representations agree well even in cases where the one-particle basis is incomplete and the TM has not converged. For BH and C2 the TM in the length representation converges rapidly with improvements in the one-particle basis set and is insensitive to inner-shell correlation. In contrast, in the velocity representation convergence with improvements in the one-particle basis is much slower, especially for C2, and the TMs are significantly changed by inner-shell correlation. Thus the difference between the TMs in the length and velocity representations would not appear to be a viable diagnostic of TM convergence. |
| |
Keywords: | Transition moments Convergence Length representation Velocity representation |
本文献已被 SpringerLink 等数据库收录! |
|