Parity-violation contribution to electric field gradient

Introduction

In this tutorial we introduce the calculation of parity violation contribution to the electric field gradient tensor as given in the DIRAC code.

As described in PROPERTIES, the parity-violation contribution to the electronic part of the electric field gradient tensor (PVCEFG) of a nucleus \(K\) is given by

\[q^{PV}_{ij} (\mathbf{R}_K) = \langle\langle \hat q_{ij} (\mathbf{R}_K); \hat{H}^{PV}_K \rangle\rangle_0\]

where the contribution from the K nucleus to the nuclear spin-independent parity-violating operator

\[\hat{H}^{PV}_K =\frac{G_F}{2\sqrt{2}}\sum_{i,K}Q_{w,K}\gamma_i^5\rho_K(\mathbf{r}_i)\]

is expressed in terms of the Fermi coupling constant \(G_F=2.222516\times 10^{-14}E_ha_0^3\) (this value corresponds to CODATA 2022, but it can change if you use other CODATA set), the weak nuclear charge \(Q_{w,K}\) and the normalized nuclear charge density \(\rho_K\) (in units of the inverse of cube distances). Results are given in a.u. Further details can be found in [Aucar2025_PVEFG].

Application to the H2O2 molecule

As an example, we show a calculation of the PV contribution to the EFG tensor of the oxygen and hydrogen nuclei at the Hydrogen peroxide molecule. The input file efg_dc.inp is given by

**DIRAC                                                                                             
.TITLE                                                                                              
 PVC to EFG
.WAVE FUNCTION
.PROPERTIES
**INTEGRALS
.SELECT
 2
 1
 3
**GENERAL
.CODATA
 CODATA22
**WAVE FUNCTIONS                                                                                    
.SCF                                                                                                
*SCF
.ERGCNV
5.0E-9
**PROPERTIES                                                                                        
.PVC
.PVCEFG
.ABUNDANCIES
 0.0001
.PRINT
  1
*END OF

whereas the molecular input file H2O2.mol is

INTGRL
H2O2 molecule
3-21G basis
C   2    0
       1.     2
H1    -0.690815           -1.726149            1.667775     isotope=1
H2     0.690815            1.726149            1.667775     isotope=1
LARGE BASIS 3-21G
       8.     2
O3     0.000000           -1.407846            0.000000     isotope=17
O4     0.000000            1.407846            0.000000     isotope=17
LARGE BASIS 3-21G
FINISH

The calculation is run using:

pam --inp=efg_dc --mol=H2O2

As a result, PVCEFG are obtained at the RPA (i.e., coupled Hartree-Fock) level of approach. The code also works at the DFT level.

Reading the output file

As the .PRINT flag in the input file is set to 1, extra details are printed. The results are given in au. The PVCEFG to the oxygen and hydrogen nuclei will look like:

      **********************************************************************
      **************** PARITY-VIOLATION CONTRIBUTION TO EFG ****************
      **********************************************************************

      According to J. J. Aucar and A. F. Maldonado,
      Parity Violation Effects on the Electric Field Gradient,
      Phys. Chem. Chem. Phys., 27, 7594 (2025)
      --------------------------------------------------------
 
@ Nuclear species:
===============================================================
@ name  charge  isotope   mass         abundance           Qw
---------------------------------------------------------------
@ H1         1        1     1.000000      99.985         0.0751
@                     2     2.000000       0.015        -0.9249
@ O3         8        1    16.000000      99.760        -7.3990
@                     2    18.000000       0.200        -9.3990
@                     3    17.000000       0.040        -8.3990
-------------------------------------------------------------

@ Selected nuclear species:
===============================================================
@ name  charge  isotope   mass         abundance           Qw
---------------------------------------------------------------
@ H1         1        1     1.000000      99.985         0.0751
@ O3         8        3    17.000000       0.040        -8.3990
-------------------------------------------------------------






===========================================================================================
  Nucleus: H1  


  Total PV contributions to EFG tensor (a.u.):
  --------------------------------------------

                   x             y             z
   x       -0.254391E-22  0.239946E-22 -0.230101E-22
   y        0.239946E-22 -0.222935E-22 -0.121943E-22
   z       -0.230101E-22 -0.121943E-22  0.477326E-22



  e-p and e-e response contributions (a.u.):
  ------------------------------------------

            x             y             z                 x             y             z
  x  0.398466E-25 -0.817881E-25  0.414748E-26     -0.254789E-22  0.240764E-22 -0.230143E-22
  y -0.817881E-25 -0.531662E-25 -0.174272E-25      0.240764E-22 -0.222404E-22 -0.121769E-22
  z  0.414748E-26 -0.174272E-25  0.133196E-25     -0.230143E-22 -0.121769E-22  0.477193E-22

===========================================================================================
  Nucleus: O3  


  Total PV contributions to EFG tensor (a.u.):
  --------------------------------------------

                   x             y             z
   x        0.770225E-17 -0.122332E-17 -0.182415E-17
   y       -0.122332E-17 -0.697042E-17 -0.454296E-17
   z       -0.182415E-17 -0.454296E-17 -0.731824E-18



  e-p and e-e response contributions (a.u.):
  ------------------------------------------

            x             y             z                 x             y             z
  x  0.144288E-19  0.482375E-20 -0.146931E-19      0.768782E-17 -0.122814E-17 -0.180945E-17
  y  0.482375E-20  0.157480E-21  0.326208E-20     -0.122814E-17 -0.697058E-17 -0.454623E-17
  z -0.146931E-19  0.326208E-20 -0.145862E-19     -0.180945E-17 -0.454623E-17 -0.717238E-18

===========================================================================================

As it can be seen, the total PVC to the EFG tensor elements is further separated in their (e-e) and (e-p) parts.

Warning

The basis set used here is rather small for demonstration purposes; larger basis sets are recommended for production calculations.