An ab Initio Calculation of the Valence Excitation Spectrum of H2O···Cl2: Comparison to Condensed Phase Spectra

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• 作者：Ricardo Franklin-Mergarejo ; Jesus Rubayo-Soneira ; Nadine Halberstadt ; Tahra Ayed ; Margarita I. Bernal Uruchurtu ; Ramn Hernndez-Lamoneda ; Kenneth C. Janda
• 刊名：Journal of Physical Chemistry A
• 出版年：2009
• 出版时间：July 2, 2009
• 年：2009
• 卷：113
• 期：26
• 页码：7563-7569
• 全文大小：247K
• 年卷期：v.113,no.26(July 2, 2009)
• ISSN：1520-5215

文摘

Valence electronic excitation spectra are calculated for the H₂O···Cl₂ dimer using state-of-the art ab initio potentials for both the ground and the valence excited states, a basis set calculation of the ground state nuclear wave funtion, and a wave packet analysis to simulate the dynamics on the excited state surface. The peak of the H₂O···Cl₂ dimer spectrum is blue-shifted by 1250 cm⁻¹ from that of the free Cl₂ molecule. This is less than the value previously estimated from vertical excitation energies but still significantly more than the blue shift in aqueous solution and clathrate−hydrate solid. Seventy percent of the blue shift is attributed to ground state stabilization, the rest to excited state repulsion. Spin−orbit effects are found to be small for this dimer. Homogeneous broadening is found to be slightly smaller for the dimer than for the free Cl₂. The reflection principle and spectrator model approximations were tested and found to be quite satisfactory. This is promising for an eventual simulation of the condensed phase spectra.