The potential energy curve of the CD(X^2Π) radical is obtained using the coupled-cluster singles-doublesapproximate-triples [CCSD(T)] theory in combination with the correlation-consistent quintuple basis set augmented with diffuse functions,aug-cc-pV5Z.The potential energy curve is fitted to the Murrell-Sorbie function,which is used to determine the spectroscopic parameters.The obtained D0,De,Re,ωe,ωeχe,αe and Be values are 3.4971 eV,3.6261 eV,0.11197 nm,2097.661 cm 1,34.6963 cm 1,0.2083 cm 1 and 7.7962 cm 1,respectively,which conform almost perfectly to the available measurements.With the potential obtained at the UCCSD(T)/aug-cc-pV5Z level of theory,a total of 24 vibrational states have been predicted for the first time when J = 0 by solving the radial Schr¨odinger equation of nuclear motion.The complete vibrational levels,the classical turning points,the inertial rotation constants and centrifugal distortion constants are reproduced from the CD(X^2Π) potential when J = 0,and are in excellent agreement with the available measurements.The total and the various partial-wave cross sections are calculated for the elastic collisions between the ground-state C and D atoms at energies from 1.0×10 11 to 1.0×10 4 a.u.when the two atoms approach each other along the CD(X^2Π) potential energy curve.Only one shape resonance is found in the total elastic cross sections,and the resonant energy is 8.36×10 6 a.u.The results show that the shape of the total elastic cross section is mainly dominated by the s partial wave at very low temperatures.Because of the weak shape resonances coming from higher partial waves,most of them are passed into oblivion by the strong total elastic cross sections.
Equilibrium internuclear separations,harmonic frequencies and potential energy curves(PECs) of HCl(X1Σ+) molecule are investigated by using the highly accurate valence internally contracted multireference configuration interaction(MRCI) approach in combination with a series of correlation-consistent basis sets in the valence range.The PECs are all fitted to the Murrell-Sorbie function,and they are used to accurately derive the spectroscopic parameters(De,D0,ωeχe,αe and Be).Compared with the available measurements,the PEC obtained at the basis set,aug-cc-pV5Z,is selected to investigate the vibrational manifolds.The constants D0,De,Re,ωe,ωeχe,αe and Be at this basis set are 4.4006 eV,4.5845 eV,0.12757 nm,2993.33 cm 1,52.6273 cm 1,0.2981 cm 1 and 10.5841 cm 1,respectively,which almost perfectly conform to the available experimental results.With the potential determined at the MRCI/aug-cc-pV5Z level of theory,by numerically solving the radial Schro¨dinger equation of nuclear motion in the adiabatic approximation,a total of 21 vibrational levels are predicted.Complete vibrational levels,classical turning points,inertial rotation and centrifugal distortion constants are reproduced,which are in excellent agreement with the available Rydberg-Klein-Rees data.Most of these theoretical vibrational manifolds are reported for the first time to the best of our knowledge.
Interaction potentials for LiCl(X 1 Σ +) are constructed by the highly accurate valence internally contracted mul-tireference configuration interaction in combination with a number of large correlation-consistent basis sets,which are used to determine the spectroscopic parameters (D 0,D e,R e,ω e,ω e χ e,B e and α e).The potentials obtained at the basis sets,i.e.,aug-cc-pV5Z-JKFI for Cl and cc-pV5Z for Li,are selected to study the elastic collision properties of Li and Cl atoms at the impact energies from 1.0×10 12 to 1.0×10 4 a.u.The derived total elastic cross sections are very large and almost constant at ultralow temperatures,and their shapes are mainly dominated by the s-partial wave at very low impact energies.Only one shape resonance can be found in the total elastic cross sections over the present collision energy regime,which is rather strong and obviously broadened by the overlap contributions of the abundant resonances coming from various partial waves.Abundant resonances exist for the elastic partial-wave cross sections until l=22 partial waves.The vibrational manifolds of the LiCl(X 1 Σ +) molecule,which are predicted at the present level of theory and the basis sets cc-pV5Z for Li and the aug-cc-pV5Z-JKFI for Cl,should achieve much high accuracy due to the employment of the large correlation-consistent basis sets.
The potential energy curve(PEC) of HI(X1Σ+) molecule is studied using the complete active space self-consistent field method followed by the highly accurate valence internally contracted multireference configuration interaction approach at the correlation-consistent basis sets,aug-cc-pV6Z for H and aug-cc-pV5Z-pp for I atom.Using the PEC of HI(X1Σ+),the spectroscopic parameters of three isotopes,HI(X1Σ+),DI(X1Σ+) and TI(X1Σ+),are determined in the present work.For the HI(X1Σ+),the values of D 0,D e,R e,ω e,ω e χ e,α e and B e are 3.1551 eV,3.2958 eV,0.16183 nm,2290.60 cm 1,40.0703 cm 1,0.1699 cm 1 and 6.4373 cm 1,respectively;for the DI(X1Σ+),the values of D 0,D e,R e,ω e,ω e χ e,α e and B e are 3.1965 eV,3.2967 eV,0.16183 nm,1626.8 cm 1,20.8581 cm 1,0.0611 cm 1 and 3.2468 cm 1,respectively;for the TI(X1Σ+),the values of D 0,D e,R e,ω e,ω e χ e,α e and B e are of 3.2144 eV,3.2967 eV,0.16183 nm,1334.43 cm 1,14.0765 cm 1,0.0338 cm 1 and 2.1850 cm 1,respectively.These results accord well with the available experimental results.With the PEC of HI(X1Σ+) molecule obtained at present,a total of 19 vibrational states are predicted for the HI,26 for the DI,and 32 for the TI,when the rotational quantum number J is equal to zero(J = 0).For each vibrational state,vibrational level G(υ),inertial rotation constant B υ and centrifugal distortion constant D υ are determined when J = 0 for the first time,which are in excellent agreement with the experimental results.
