Tong Xin, Cerný Jirí, Müller-Dethlefs Klaus
The Photon Science Institute, Alan Turing Building, the School of Chemistry, The University of Manchester, UK.
J Phys Chem A. 2008 Jul 3;112(26):5872-7. doi: 10.1021/jp710998m. Epub 2008 Jun 6.
Clusters of Ar bound to isomers of the aromatic hydrocarbon n-butylbenzene (BB) have been studied using two-color REMPI (resonance enhanced multiphoton ionization) and MATI (mass analyzed threshold ionization) spectroscopy to explore noncovalent vdW interactions between these two moieties. Blue shifts of excitation energy were observed for gauche-BB...Ar clusters, and red shifts for anti-BB...Ar clusters were observed. Adiabatic ionization energies (IEs) of the conformer BB-I...Ar and BB-V...Ar were determined as 70052 and 69845 +/- 5 cm (-1), respectively. Spectral features and vibrational modes were interpreted with the aid of UMP2/cc-pVDZ ab initio calculations. Data of complexation shifts of the alkyl-benzenes and their argon clusters were collected and discussed. Using the CCSD(T) method at complete basis set (CBS) level, interaction energies for the neutral ground states of BB-I...Ar and BB-V...Ar were obtained as 650 and 558 cm (-1), respectively. Combining the CBS calculation results and the REMPI and MATI spectra allowed further the determination of the interaction energies and the energetics of BB...Ar in the excited neutral S 1 and the D 0 cationic ground states.
利用双色共振增强多光子电离（REMPI）和质量分析阈值电离（MATI）光谱研究了与芳烃正丁基苯（BB）异构体结合的氩团簇，以探索这两个部分之间的非共价范德华相互作用。观察到gauche-BB...Ar团簇的激发能蓝移，以及anti-BB...Ar团簇的激发能红移。确定构象体BB-I...Ar和BB-V...Ar的绝热电离能（IEs）分别为70052和69845±5 cm⁻¹。借助UMP2/cc-pVDZ从头算计算对光谱特征和振动模式进行了解释。收集并讨论了烷基苯及其氩团簇的络合位移数据。在完整基组（CBS）水平上使用CCSD（T）方法，得到BB-I...Ar和BB-V...Ar中性基态的相互作用能分别为650和558 cm⁻¹。结合CBS计算结果以及REMPI和MATI光谱，进一步确定了激发态中性S₁和D₀阳离子基态下BB...Ar的相互作用能和能量学。
