A reanalysis of the k3Π state of CO

Abstract

Articles you may be interested inA critical re-assignment of the Rydberg states of iodomethane based on new polarization data J. Chem. Phys. 138, 134308 (2013); 10.1063/1.4798972[1 + 1] photodissociation of CS 2 + ( X ̃ 2 Π g ) via the vibrationally mediated B ̃ 2 Σ u + state: Multichannels exhibiting and mode specific dynamicsThe k 3 ⌸ state of the CO molecule is investigated in the region between 91 000 and 97 000 cm Ϫ1 via 1ϩ1 resonance enhanced multiphoton ionization spectroscopy on CO molecules prepared in a single quantum level of the a 3 ⌸(vϭ1͒ state. A new vibronic band is found which is at lower energy than the vibrational ground state reported in the literature, leading to a reassignment of the vibrational numbering of the k 3 ⌸ state. The rotationally resolved spectra of the k 3 ⌸ (vϭ0-6͒ ←a 3 ⌸(vϭ1, Jϭ1, ⍀ϭ1͒ of 12 CO and 13 CO have been observed and analyzed, confirming the new vibrational labeling and providing a full set of molecular constants of the k 3 ⌸ valence state.

Orbital-free embedding applied to the calculation of induced dipole moments in CO2⋯X (X=He, Ne, Ar, Kr, Xe, Hg) van der Waals complexes

“…Mazeau et al 13 also identified another feature at 94 245± 81 cm −1 ͑11.685± 0.01 eV-their feature b͒, under different electron energy and scattering angles, which can now be associated with the k 3 ⌸ ͑v =5͒ state. 16,20 The difference between their term value and the location of the k -X ͑5-0͒ observed in this study at Ϸ94 437 cm −1 lies somewhat outside of the estimated experimental error by Mazeau et al Table IV. The other study requires a more detailed consideration as it appears to be inconsistent with our study.…”

“…As previously mentioned the band shown in Fig. 2 20 As described in the Introduction, Berden et al 20 performed a 1 + 1 REMPI study on metastable a 3 ⌸ CO molecules. Three lines corresponding to 1 + 1 REMPI via the k 3 ⌸ ͑v =5͒ state of CO molecules, initially prepared in the a 3 ⌸ ͑v =1, J =1, ⍀ =1, f parity͒ state, were identified and assigned.…”

“…However, these three lines were accompanied by six extra ionization lines, which were not assigned. Table I gives the term values of the three assigned upper-state levels of the k 3 ⌸ ͑v =5͒ state derived from Berden et al 20 It seems clear that the new absorption band observed at Ϸ94 437 cm −1 is assignable to the k -X ͑5-0͒ transition. Its structure somewhat resembles the k -X ͑3-0͒ and k -X ͑4-0͒ absorption bands 17 and it occurs in the correct transition energy region.…”

“…This will be shown more clearly below. Berden et al 20 Rotational assignment of the 94 225 cm −1 band was, as for the k -X ͑5-0͒ band, a nontrivial matter. Past spectroscopic studies of the v = 0 level of the c 3 ⌸ state show the state to be approximately of Hund's case b coupling and branches of the c -X ͑1-0͒ band will be characterized by ⌬N and ⌬J, where N and J are the electron spin and total, rotational quantum numbers, respectively, and the rotational branches are labeled as ⌬N ⌬J.…”

“…There have been several spectroscopic studies on the k 3 ⌸ valence state. [16][17][18][19][20][21] Berden et al 20 showed that the vibrational labeling of the k 3 ⌸ state in studies prior to 1997 needed to be incremented by one unit. In that study metastable a 3 ⌸ ͑v =1͒ state CO molecules were prepared predominantly in the J = 1 rotational level via pulsed narrowband laser excitation of jet-cooled ground-state CO molecules.…”