Calculating splittings between energy levels of different symmetry using path-integral methods.
نویسندگان
چکیده
It is well known that path-integral methods can be used to calculate the energy splitting between the ground and the first excited state. Here we show that this approach can be generalized to give the splitting patterns between all the lowest energy levels from different symmetry blocks that lie below the first-excited totally symmetric state. We demonstrate this property numerically for some two-dimensional models. The approach is likely to be useful for computing rovibrational energy levels and tunnelling splittings in floppy molecules and gas-phase clusters.
منابع مشابه
Perturbative Approach to Calculating the Correlation Function of bi-isotropic Metamaterials
A bi-isotropic magneto-electric metamaterials is modeled by two independent reservoirs. The reservoirs contain a continuum of three dimensional harmonic oscillators, which describe polarizability and magnetizability of the medium. The paper aimed to investigate the effect of electromagnetic field on bi-isotropic. Starting with a total Lagrangian and using Euler-Lagrange equation, researcher cou...
متن کاملSpin Tunneling in Molecular Magnets
We study spin tunneling in magnetic molecules, with special reference to Fe8. The article aims to give a pedagogical discussion of what is meant by the tunneling of a spin, and how tunneling amplitudes or energy level splittings may be calculated using path integral and discrete phase integral methods. In the case of Fe8, an issue of great interest is the oscillatory tunnel splittings as a func...
متن کاملAnalytic Treatment of Positronium Spin Splittings in Light-Front QED
We study the QED bound-state problem in a light-front hamiltonian approach. Starting with a bare cutoff QED Hamiltonian, H B , with matrix elements between free states of drastically different energies removed, we perform a similarity transformation that removes the matrix elements between free states with energy differences between the bare cutoff, Λ, and effective cutoff, λ (λ < Λ). This gene...
متن کاملQuantum tunneling splittings from path-integral molecular dynamics.
We illustrate how path-integral molecular dynamics can be used to calculate ground-state tunnelling splittings in molecules or clusters. The method obtains the splittings from ratios of density matrix elements between the degenerate wells connected by the tunnelling. We propose a simple thermodynamic integration scheme for evaluating these elements. Numerical tests on fully dimensional malonald...
متن کاملElectronic effects on singlet-triplet energy splittings in aryl-cyclopentadienylidenes
Energy gaps, AXsar (X=E, H and G) (AX.,.,-=lia,„,,,InrX“dpka,) between single (s) and triplet (I) states werecalculated at B3LTP/6-3 I 1.HO" level of theory. Our results showed that electron donating substituents(G = -NHz, -OH. -CH), -F, -Cl and -Br) at phenyl group cause to increase and electron withdrawingsubstiluents (G -CF2. and -NO:) lead to decrease the singlet-triplet energy gaps of Ar -...
متن کاملذخیره در منابع من
با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید
برای دانلود متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید
ثبت ناماگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید
ورودعنوان ژورنال:
- The Journal of chemical physics
دوره 144 11 شماره
صفحات -
تاریخ انتشار 2016