Rovibrational states of ClHCl- isotopologues up to high J: a joint theoretical and spectroscopic investigation.
نویسندگان
چکیده
Explicitly correlated coupled cluster theory at the CCSD(T*)-F12b level (T. B. Adler, G. Knizia, and H.-J. Werner, J. Chem. Phys., 2007, 127, 221106) and two precise spectroscopic parameters (K. Kawaguchi, J. Chem. Phys., 1988, 88, 4186) were used to construct an accurate near-equilibrium analytical potential energy function (PEF) for the highly anharmonic centrosymmetric hydrogen-bonded complex ClHCl(-) (Re = 3.1153 Å). From variational calculations with that PEF, a large number of rovibrational energies of different isotopologues up to high values of the rotational quantum number J was obtained. Theory helped with the assignment of lines observed by IR diode laser spectroscopy in the ν1 + ν3 combination band of (35)ClH(35)Cl(-) and (37)ClH(35)Cl(-) and enabled us to elucidate rather subtle patterns of rovibrational interactions. Furthermore, transition dipole moments were predicted and analysed as well as unusual isotopic effects.
منابع مشابه
Nonequilibrium rovibrational energy distributions of hydrogen isotopologues in an expanding plasma jet.
State resolved densities of high rovibrationally excited hydrogen isotopologues H(2), HD, and D(2) in the electronic ground state have been measured in a supersonically expanding plasma jet. The obtained state distributions differ substantially from thermal equilibrium. Moreover, the distributions are not the same for H(2), HD, and D(2) indicating different formation and relaxation rates for ea...
متن کاملRovibrational quantum dynamical computations for deuterated isotopologues of the methane-water dimer.
Rovibrational states of four dimers formed by the light and the heavy isotopologues of the methane and water molecules are computed using a potential energy surface taken from the literature. The general rovibrational energy-level pattern characteristic to all systems studied is analyzed employing two models of a dimer: the rigidly rotating complex and the coupled system of two rigidly rotating...
متن کاملSynthesis, spectroscopic (NMR and FT-IR) and theoretical (HF and DFT) investigation of dimethyl (Z)-2-[(2-methyl-5-oxo-1-cyclopentyl)oxy]-2-butendioate
Dimethyl (z)-2-[(2-methyl-5-oxo-1-cyclopentyl)oxy]-2-butenedioate has been synthesized using one-pot three component reaction between N-isocyaniminotriphenylphosphorane (Ph3PNNC), 3-methylcyclopentene-1,2-dione and dimethyl acetylenedicarboxylate. Also, optimized geometry and nuclear magnetic resonance ( NMR ) of the title compound are evaluated using HF and B3LYP methods and 6-311+G(d) basis s...
متن کاملVariational quantum mechanical and active database approaches to the rotational-vibrational spectroscopy of ketene, H2CCO.
A variational quantum mechanical protocol is presented for the computation of rovibrational energy levels of semirigid molecules using discrete variable representation of the Eckart-Watson Hamiltonian, a complete, "exact" inclusion of the potential energy surface, and selection of a vibrational subspace. Molecular symmetry is exploited via a symmetry-adapted Lanczos algorithm. Besides symmetry ...
متن کاملPeaking Attenuation in High-Gain Observers Using Adaptive Saturation: Application to a Ball and Wheel System
Despite providing robustness, high-gain observers impose a peaking phenomenon, which may cause instability, on the system states. In this paper, an adaptive saturation is proposed to attenuate the undesirable mentioned phenomenon in high-gain observers. A real-valued and differentiable sigmoid function is considered as the saturating element whose parameters (height and slope) are adaptively tu...
متن کاملذخیره در منابع من
با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید
عنوان ژورنال:
- Physical chemistry chemical physics : PCCP
دوره 15 18 شماره
صفحات -
تاریخ انتشار 2013