jp710998m_si_001.pdf (66.51 kB)

Effect of Noncovalent Interactions on the n-Butylbenzene···Ar Cluster Studied by Mass Analyzed Threshold Ionization Spectroscopy and ab initio Computations

Download (66.51 kB)
journal contribution
posted on 03.07.2008 by Xin Tong, Jiří Černý, Klaus Müller-Dethlefs
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 S1 and the D0 cationic ground states.