7.10 Coupled-Cluster Excited-State and Open-Shell Methods

7.10.9 Auger Spectra and Lifetimes of Core-Level States

(June 30, 2021)

Certain types of resonances can be described by using real-valued EOM-CC wave functions via Feshbach-Fano approach. 310 Feshbach H.
Ann. Phys.
(1962), 19, pp. 287.
Link
, 304 Fano U.
Phys. Rev.
(1961), 124, pp. 1866.
Link
In this section we describe the application of Feshbach-Fano approach to core-excited and core-ionized states. 1006 Skomorowski W., Krylov A.I.
J. Chem. Phys.
(2021), 154, pp. 084124.
Link
, 1007 Skomorowski W., Krylov A.I.
J. Chem. Phys.
(2021), 154, pp. 084125.
Link
Core-hole states, which are Feshbach resonances, are subject to autoionization—commonly known as Auger decay. Auger Electron Spectroscopy (AES) measures kinetic energy and intensity of ejected electrons. Theoretical description of AES can be formulated using Feshbach-Fano approach for electronic resonances. 310 Feshbach H.
Ann. Phys.
(1962), 19, pp. 287.
Link
, 304 Fano U.
Phys. Rev.
(1961), 124, pp. 1866.
Link
The theory invokes two projection operators, Q^ and P^, which decompose the total wavefunction into bound-like and continuum-like components. In the case of core-level states this separation is enabled by invoking the CVS scheme and frozen-core approximation in the calculations of initial and final states in the Auger process (more details about CVS can be found in Section 7.10.7).

The initial (bound-like) state Ψ0 is a core-hole ionized or core-hole excited state, which can be described by CVS-EOM-CC. The final (continuum-like) state χμ,Ek is represented as an antisymmetrized product of a stable channel state Ψμ (described by an appropriate EOM-EE model) and a continuum orbital ϕk, χμ,Ek𝒜{ϕkΨμ}. Note that Ψμ is a state with one electron less than Ψ0. Two essential parameters defining AES are the rate of the decay into a channel μ, given as

Γμ=2πΨ0L|H^-E0|χμ,EkRχμ,EkL|H^-E0|Ψ0R, (7.62)

and partial energy correction Δμ to the zero-order resonance position E0, defined as

Δμ=P.V.0Ψ0L|H^-E0|χμ,ERχμ,EL|H^-E0|Ψ0RE0-Eμ-E𝑑E. (7.63)

In the expressions above H^ is the electronic Hamiltonian, Eμ is the energy of the channel state Ψμ, Ek is the energy of the ejected electron (Ek=E0-Eμ), L/R superscripts denote left and right EOM-CCSD wavefunctions, and P.V. stands for the Cauchy principle value. Calculations of Γμ are activated with the CC_DO_FESHBACH keyword. By default, the continuum orbital ϕk is approximated with a plane wave. 1006 Skomorowski W., Krylov A.I.
J. Chem. Phys.
(2021), 154, pp. 084124.
Link
, 1007 Skomorowski W., Krylov A.I.
J. Chem. Phys.
(2021), 154, pp. 084125.
Link
It is also possible to model ϕk with a Coulomb wave by setting CC_FESHBACH_CW = 1. This option requires to include in the input an additional input section $coulomb_wave, which provides an expansion of the Coulomb wave (for the given effective charge and kinetic energy) in terms of products of a plane wave and Gaussian-type functions, as detailed in Ref. 1006.

For non-resonant Auger decay, the initial state can be conveniently computed by CVS-EOM-IP-CCSD, whereas its stable decay channels can be obtained from EOM-DIP-CCSD calculations. Section of the input invoking Auger decay rates calculation for an atom can be given as:

$rem
jobtype = sp
method = eom-ccsd
basis = 6-31G*
cvs_eom_ip_beta [1,0,0,0,0,0,0,0] !This is the initial core-hole state
dip_triplets [0,0,0,0,0,1,1,1] !These are the final triplet decay channels
dip_singlets [3,1,1,1,0,1,1,1] !These are the final singlet decay channels
cc_do_dyson 1 !Needed for Feshbach-type calculations
cc_do_feshbach 1
$end

In resonant Auger decay, the initial state can be computed by CVS-EOM-EE-CCSD, whereas the corresponding decay channels can be obtained from EOM-IP-CCSD calculations. By default, Feshbach calculations are performed for all possible state pairs that include an energetically allowed decay channel. This is not practical if, for example, the core-hole state of interest is not the lowest state in the given symmetry, or when the Coulomb wave is used to model the continuum orbital. In such a case, the user can specify pairs of states for Feshbach calculations using $trans_prop section with dyson as the requested property:

$trans_prop
   state_list
   cvs_ip_beta 1 1 !state 1: CVS_IP with irrep = 1 and istate = 1
   dip_singlets 1 3 !state 2: DIP_SINGLET state with irrep = 1 and istate = 3
   dip_triplets 6 1 !state 3: DIP_TRIPLET state with irrep = 6 and istate = 1
   end_list
   state_pair_list
   1 2   ! transition 1 <-> 2
   1 3   ! transition 1 <-> 3
   end_pairs
   calc dyson
$end

Calculations of energy correction Δμ are invoked by setting CC_DO_FESHBACH = 2, and are currently available only within the plane-wave approximation.

The integrals in Eq. (7.62) are evaluated analytically. Integration in Eq. (7.63) is done numerically, and is split into two or three intervals to bypass the singularity at E=E0-Eμ. The upper limits of those intervals are set to default values related to E0. They can also be customized (except for the first interval) by setting CC_FESHBACH_DELTA_INTB = XX and/or CC_FESHBACH_DELTA_INTC = YY where XX and/or YY are desired upper integration limits in units of eV.

CC_DO_FESHBACH
       Activates calculation of resonance widths using Feshbach-Fano approach.
TYPE:
       INTEGER
DEFAULT:
       0
OPTIONS:
       0 do not invoke Feshbach-Fano calculation 1 invoke Feshbach-Fano calculation of the resonance width 2 invoke Feshbach-Fano calculation of the resonance width and resonance shift
RECOMMENDATION:
       Initial and final states should be correctly specified.

CC_FESHBACH_CW
       Activates Coulomb wave description of the ejected electron.
TYPE:
       INTEGER
DEFAULT:
       0
OPTIONS:
       0 Use plane wave 1 Use Coulomb wave
RECOMMENDATION:
       Additional details need to be specified in $coulomb_wave section.

CC_FESHBACH_DELTA_INTB
       Specifies integration limits in calculation of energy shift in Feshbach-Fano calculations.
TYPE:
       INTEGER
DEFAULT:
       Preset
OPTIONS:
       n corresponds to energy limit in eV
RECOMMENDATION:
       Use default.

CC_FESHBACH_DELTA_INTC
       Specifies integration limits in calculation of energy shift in Feshbach-Fano calculations.
TYPE:
       INTEGER
DEFAULT:
       Preset
OPTIONS:
       n corresponds to energy limit in eV
RECOMMENDATION:
       Use default.

7.10.9.1 Examples

Examples 7.10.9.1 and 7.10.9.1 illustrate calculation of resonant Auger decay of core-ionized water molecule. The initial state is described by CVS-EOM-IP-CCSD and the decay channels are described by EOM-DIP-CCSD. Example 7.10.9.1 uses a plane-wave representation of the ejected electron. In example 7.10.9.1, the autoionizing electron is described by the Coulomb wave, represented by a pseudo-partial wave expansion over PW-CGTO functions.

Example 7.47  Calculation of Auger decay rates of core-ionized water molecule to selected singlet and triplet final states. Continuum orbital is a plane wave.

$molecule
0 1
   O         0.0000    0.000    0.0000
   H        -0.7528    0.000   -0.5917
   H         0.7528    0.000   -0.5917
$end

$rem
   METHOD            ccsd
   BASIS             6-311+G(3df)
   CVS_EOM_IP_BETA   [1,0,0,0]
   DIP_SINGLETS      [4,1,2,2]
   DIP_TRIPLETS      [1,1,2,2]
   CC_DO_DYSON       1
   CC_DO_FESHBACH    1
$end

View output

Example 7.48  Calculation of Auger decay rates of core-ionized water molecule to selected singlet and triplet final states. Continuum orbital is approximated by a Coulomb wave.

$molecule
0 1
   O         0.0000    0.000    0.0000
   H        -0.7528    0.000   -0.5917
   H         0.7528    0.000   -0.5917
$end

$rem
   METHOD            ccsd
   BASIS             6-311+G(3df)
   CVS_EOM_IP_BETA   [1,0,0,0]
   DIP_TRIPLETS      [1,1,2,2]
   CC_DO_DYSON       1
   CC_DO_FESHBACH    1
   CC_FESHBACH_CW    1
$end

$trans_prop
state_list
  cvs_ip_beta  1 1
  dip_triplets 3 2
end_list
state_pair_list
  1 2   ! transition 1 <-> 2
end_pairs
calc dyson
$end

$coulomb_wave
!This PW-CGTO expansion of CW is optimized for Z = 4.9 and Ek = 475.7 eV
!CW is centered on oxygen (atom #1), has Lmax = 2, and n = 4 GTOs for each L
1 2 4
!List of GTO exponents for each consecutive pseudo-partial wave from L = 0 to Lmax
33.92543607
 0.85503320
 0.03878479
 0.00464513
10.09805405
 0.75935967
 0.06727680
 0.00646507
 6.96653113
 0.94413668
 0.11599464
 0.01425085
!List of corresponding GTO contraction coefficients - real and imaginary parts
 1.15237075   -1.28233348
 0.96764647   -0.30588374
 0.94868507    0.99338435
-1.18258037   -0.06876149
-0.62304129    0.90336892
-0.14457938    0.18631218
-0.07528422    0.01001695
-0.00950295   -0.02658981
 0.22796804   -0.19298801
 0.01268528   -0.03579628
 0.00369451   -0.00318780
 0.00068338    0.00016431
$end

View output