Yang Maoping, Zhang Limin, Zhuang Xiujuan, Lai Likun, Yu Shuqin
Department of Chemical Physics, University of Science and Technology of China, Hefei, Anhui 230026, Peoples Republic of China.
J Chem Phys. 2008 Apr 28;128(16):164308. doi: 10.1063/1.2905232.
In the wavelength range of 235-354 nm, we have obtained the mass-resolved [1+1] two-photon dissociation spectra of CO(2) (+) via A (2)Pi(u,12)(upsilon(1)upsilon(2)0)<--X (2)Pi(g,12)(000) transitions by preparing CO(2) (+) ions in the X (2)Pi(g,12)(000) state via [3+1] multiphoton ionization of CO(2) molecules at 333.06 nm. The vibronic bands of (upsilon(1)20;upsilon(1)=0-11)micro (2)Pi(12) and (upsilon(1)20;upsilon(1)=0-6)kappa (2)Pi(12) involving the bending mode of CO(2) (+)(A (2)Pi(u,12)) were assigned. The spectroscopic constants of T(e)=27 908.9+/-1.1 cm(-1) [above CO(2) (+)(X (2)Pi(g,12))], nu(1)=1126.00+/-0.36 cm(-1), chi(11)=-1.602+/-0.005 cm(-1), nu(2)(micro (2)Pi(12))=402.5+/-13.3 cm(-1), and nu(2)(kappa (2)Pi(12))=493.1+/-23.6 cm(-1) for CO(2) (+)(A (2)Pi(u,12)) are deduced from the data of the A (2)Pi(u,12)(upsilon(1)upsilon(2)0)<--X (2)Pi(g,12)(000) transitions. The observed intensity reversal between (500) (2)Pi(12) and (420)micro (2)Pi(12) can be attributed to the conformational variation of CO(2) (+)(A (2)Pi(u,12)) from linear to bent, then the conversion potential barrier is estimated to be 5209 cm(-1) above CO(2) (+)(A (2)Pi(u,12)(000)). The wavelength and level dependence of the photofragment branching ratios have been measured and the dissociation dynamics of CO(2) (+) via A (2)Pi(u,12) state is discussed.
