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# 7.10.18 Equation-of-Motion Coupled-Cluster Job Control

(February 4, 2022)

It is important to ensure there are sufficient resources available for the necessary integral calculations and transformations. For CCMAN/CCMAN2 algorithms, these resources are controlled using the $rem variables CC_MEMORY, MEM_STATIC and MEM_TOTAL (see Section 6.16). The exact flavor of correlation treatment within equation-of-motion methods is defined by METHOD (see Section 7.1). For EOM-CCSD, once should set METHOD to EOM-CCSD, for EOM-MP2, METHOD = EOM-CCSD, etc.. In addition, a specification of the number of target states is required through XX_STATES (XX designates the type of the target states, e.g., EE, SF, IP, EA, DIP, DSF, etc.). Users must be aware of the point group symmetry of the system being studied and also the symmetry of the initial and target states of interest, as well as symmetry of transition. It is possible to turn off the use of symmetry by CC_SYMMETRY. If set to FALSE the molecule will be treated as having $C_{1}$ symmetry and all states will be of $A$ symmetry. Note: 1. In finite-difference calculations, the symmetry is turned off automatically, and the user must ensure that XX_STATES is adjusted accordingly. 2. In CCMAN, mixing different EOM models in a single calculation is only allowed in Dyson orbitals calculations. In CCMAN2, different types of target states can be requested in a single calculation. ## 7.10.18.1 Alternative way to set up EOM calculations Below we describe alternative way to specify correlation treatment in EOM-CC/CI calculations. These keywords will be eventually phased out. By default, the level of correlation of the EOM part of the wave function (i.e., maximum excitation level in the EOM operators $R$) is set to match CORRELATION, however, one can mix different correlation levels for the reference and EOM states by using EOM_CORR. To request a CI calculation, set CORRELATION = CI and select type of CI expansion by EOM_CORR. The table below shows default and allowed CORRELATION and EOM_CORR combinations. Table 7.2 shows the correct combinations of CORRELATION and EOM_CORR for standard EOM and CI models. The most relevant EOM-CC input options follow. EE_STATES EE_STATES Sets the number of excited state roots to find. For closed-shell reference, defaults into EE_SINGLETS. For open-shell references, specifies all low-lying states. TYPE: INTEGER/INTEGER ARRAY DEFAULT: 0 Do not look for any excited states. OPTIONS: $[i,j,k\ldots]$ Find $i$ excited states in the first irrep, $j$ states in the second irrep etc. RECOMMENDATION: None EE_SINGLETS EE_SINGLETS Sets the number of singlet excited state roots to find. Valid only for closed-shell references. TYPE: INTEGER/INTEGER ARRAY DEFAULT: 0 Do not look for any excited states. OPTIONS: $[i,j,k\ldots]$ Find $i$ excited states in the first irrep, $j$ states in the second irrep etc. RECOMMENDATION: None EE_TRIPLETS EE_TRIPLETS Sets the number of triplet excited state roots to find. Valid only for closed-shell references. TYPE: INTEGER/INTEGER ARRAY DEFAULT: 0 Do not look for any excited states. OPTIONS: $[i,j,k\ldots]$ Find $i$ excited states in the first irrep, $j$ states in the second irrep etc. RECOMMENDATION: None SF_STATES SF_STATES Sets the number of spin-flip target states roots to find. TYPE: INTEGER/INTEGER ARRAY DEFAULT: 0 Do not look for any excited states. OPTIONS: $[i,j,k\ldots]$ Find $i$ SF states in the first irrep, $j$ states in the second irrep etc. RECOMMENDATION: None DSF_STATES DSF_STATES Sets the number of doubly spin-flipped target states roots to find. TYPE: INTEGER/INTEGER ARRAY DEFAULT: 0 Do not look for any DSF states. OPTIONS: $[i,j,k\ldots]$ Find $i$ doubly spin-flipped states in the first irrep, $j$ states in the second irrep etc. RECOMMENDATION: None IP_STATES IP_STATES Sets the number of ionized target states roots to find. By default, $\beta$ electron will be removed (see EOM_IP_BETA). TYPE: INTEGER/INTEGER ARRAY DEFAULT: 0 Do not look for any IP states. OPTIONS: $[i,j,k\ldots]$ Find $i$ ionized states in the first irrep, $j$ states in the second irrep etc. RECOMMENDATION: None IP_ALPHA IP_ALPHA Sets the number of ionized target states derived by removing $\alpha$ electron (M${}_{s}=-{{1}\over{2}}$). TYPE: INTEGER/INTEGER ARRAY DEFAULT: 0 Do not look for any IP/$\alpha$ states. OPTIONS: $[i,j,k\ldots]$ Find $i$ ionized states in the first irrep, $j$ states in the second irrep etc. RECOMMENDATION: None IP_BETA IP_BETA Sets the number of ionized target states derived by removing $\beta$ electron (M${}_{s}$=${{1}\over{2}}$, default for EOM-IP). TYPE: INTEGER/INTEGER ARRAY DEFAULT: 0 Do not look for any IP/$\beta$ states. OPTIONS: $[i,j,k\ldots]$ Find $i$ ionized states in the first irrep, $j$ states in the second irrep etc. RECOMMENDATION: None EA_STATES EA_STATES Sets the number of attached target states roots to find. By default, $\beta$ electron will be attached (see EA_BETA). TYPE: INTEGER/INTEGER ARRAY DEFAULT: 0 Do not look for any EA states. OPTIONS: $[i,j,k\ldots]$ Find $i$ EA states in the first irrep, $j$ states in the second irrep etc. RECOMMENDATION: None EA_ALPHA EA_ALPHA Sets the number of attached target states derived by attaching $\alpha$ electron (M${}_{s}$=${{1}\over{2}}$, default in EOM-EA). TYPE: INTEGER/INTEGER ARRAY DEFAULT: 0 Do not look for any EA states. OPTIONS: $[i,j,k\ldots]$ Find $i$ EA states in the first irrep, $j$ states in the second irrep etc. RECOMMENDATION: None EA_BETA EA_BETA Sets the number of attached target states derived by attaching $\beta$ electron (M${}_{s}$=$-{{1}\over{2}}$, EA-SF). TYPE: INTEGER/INTEGER ARRAY DEFAULT: 0 Do not look for any EA states. OPTIONS: $[i,j,k\ldots]$ Find $i$ EA states in the first irrep, $j$ states in the second irrep etc. RECOMMENDATION: None DIP_STATES DIP_STATES Sets the number of DIP roots to find. For closed-shell reference, defaults into DIP_SINGLETS. For open-shell references, specifies all low-lying states. TYPE: INTEGER/INTEGER ARRAY DEFAULT: 0 Do not look for any DIP states. OPTIONS: $[i,j,k\ldots]$ Find $i$ DIP states in the first irrep, $j$ states in the second irrep etc. RECOMMENDATION: None DIP_SINGLETS DIP_SINGLETS Sets the number of singlet DIP roots to find. Valid only for closed-shell references. TYPE: INTEGER/INTEGER ARRAY DEFAULT: 0 Do not look for any singlet DIP states. OPTIONS: $[i,j,k\ldots]$ Find $i$ DIP singlet states in the first irrep, $j$ states in the second irrep etc. RECOMMENDATION: None DIP_TRIPLETS DIP_TRIPLETS Sets the number of triplet DIP roots to find. Valid only for closed-shell references. TYPE: INTEGER/INTEGER ARRAY DEFAULT: 0 Do not look for any DIP triplet states. OPTIONS: $[i,j,k\ldots]$ Find $i$ DIP triplet states in the first irrep, $j$ states in the second irrep etc. RECOMMENDATION: None DIP_AA_STATES DIP_AA_STATES Sets the number of M${}_{s}$=-1 DIP roots (remove two $\alpha$ electrons) to find. Valid only for closed-shell references. TYPE: INTEGER/INTEGER ARRAY DEFAULT: 0 Do not look for any DIP M${}_{s}$=-1 states. OPTIONS: $[i,j,k\ldots]$ Find $i$ DIP states in the first irrep, $j$ states in the second irrep etc. RECOMMENDATION: None DIP_BB_STATES DIP_BB_STATES Sets the number of M${}_{s}$=+1 DIP roots (remove two $\beta$ electrons) to find. TYPE: INTEGER/INTEGER ARRAY DEFAULT: 0 Do not look for any DIP M${}_{s}$=+1 states. OPTIONS: $[i,j,k\ldots]$ Find $i$ DIP states in the first irrep, $j$ states in the second irrep etc. RECOMMENDATION: None DIP_AB_STATES DIP_AB_STATES Sets the number of M${}_{s}$=0 DIP roots (remove one $\alpha$ and one $\beta$ electron) to find. TYPE: INTEGER/INTEGER ARRAY DEFAULT: 0 Do not look for any DIP M${}_{s}$=0 states. OPTIONS: $[i,j,k\ldots]$ Find $i$ DIP states in the first irrep, $j$ states in the second irrep etc. RECOMMENDATION: None DEA_STATES DEA_STATES Sets the number of DEA roots to find. For closed-shell reference, defaults into DEA_SINGLETS. For open-shell references, specifies all low-lying states. TYPE: INTEGER/INTEGER ARRAY DEFAULT: 0 Do not look for any DEA states. OPTIONS: $[i,j,k\ldots]$ Find $i$ DIP states in the first irrep, $j$ states in the second irrep etc. RECOMMENDATION: None DEA_SINGLETS DEA_SINGLETS Sets the number of singlet DEA roots to find. Valid only for closed-shell references. TYPE: INTEGER/INTEGER ARRAY DEFAULT: 0 Do not look for any singlet DEA states. OPTIONS: $[i,j,k\ldots]$ Find $i$ DEA singlet states in the first irrep, $j$ states in the second irrep etc. RECOMMENDATION: None DEA_TRIPLETS DEA_TRIPLETS Sets the number of triplet DEA roots to find. Valid only for closed-shell references. TYPE: INTEGER/INTEGER ARRAY DEFAULT: 0 Do not look for any DEA triplet states. OPTIONS: $[i,j,k\ldots]$ Find $i$ DEA triplet states in the first irrep, $j$ states in the second irrep etc. RECOMMENDATION: None DEA_AA_STATES DEA_AA_STATES Sets the number of M${}_{s}$=1 DEA roots (two $\alpha$ electrons) to find. TYPE: INTEGER/INTEGER ARRAY DEFAULT: 0 Do not look for any DEA M${}_{s}$=1 transitions. OPTIONS: $[i,j,k\ldots]$ Find $i$ DEA $\alpha\alpha$ states in the first irrep, $j$ states in the second irrep etc. RECOMMENDATION: None DEA_BB_STATES DEA_BB_STATES Sets the number of M${}_{s}$=-1 DEA roots (two $\beta$ electrons) to find. TYPE: INTEGER/INTEGER ARRAY DEFAULT: 0 Do not look for any DEA M${}_{s}$=-1 transitions. OPTIONS: $[i,j,k\ldots]$ Find $i$ DEA $\beta\beta$ states in the first irrep, $j$ states in the second irrep etc. RECOMMENDATION: None DEA_AB_STATES DEA_AB_STATES Sets the number of M${}_{s}$=0 DEA roots (one $\alpha$ and one $\beta$ electron) to find. TYPE: INTEGER/INTEGER ARRAY DEFAULT: 0 Do not look for any DEA M${}_{s}$=0 transitions. OPTIONS: $[i,j,k\ldots]$ Find $i$ DEA $\alpha\beta$ states in the first irrep, $j$ states in the second irrep etc. RECOMMENDATION: None Note: It is a symmetry of a transition rather than that of a target state which is specified in excited state calculations. The symmetry of the target state is a product of the symmetry of the reference state and the transition. For closed-shell molecules, the former is fully symmetric and the symmetry of the target state is the same as that of transition, however, for open-shell references this is not so. Note: In earlier versions of Q-Chem, we used EOM_XX_STATES. These keywords were replaced by XX_STATES for uniformity (e.g., they are also used in ADC methods to specify target ADC states). For backward compatibility, the old keywords are aliased to the new ones, so old inputs would still work. However, these old keywords eventually will be depreciated. It is recommended to switch to the new ones. Note: For the XX_STATES options, Q-Chem will increase the number of roots if it suspects degeneracy, or change it to a smaller value, if it cannot generate enough guess vectors to start the calculations. EOM_FAKE_IPEA EOM_FAKE_IPEA If TRUE, calculates fake EOM-IP or EOM-EA energies and properties using the diffuse orbital trick. Default for EOM-EA and Dyson orbital calculations in CCMAN. TYPE: LOGICAL DEFAULT: FALSE (use proper EOM-IP code) OPTIONS: FALSE, TRUE RECOMMENDATION: None. This feature only works for CCMAN. Note: When EOM_FAKE_IPEA is set to TRUE, it can change the convergence of Hartree-Fock iterations compared to the same job without EOM_FAKE_IPEA, because a very diffuse basis function is added to a center of symmetry before the Hartree-Fock iterations start. For the same reason, BASIS2 keyword is incompatible with EOM_FAKE_IPEA. In order to read Hartree-Fock guess from a previous job, you must specify EOM_FAKE_IPEA (even if you do not request for any correlation or excited states) in that previous job. Currently, the second moments of electron density and Mulliken charges and spin densities are incorrect for the EOM-IP/EA-CCSD target states. EOM_USER_GUESS EOM_USER_GUESS Specifies if user-defined guess will be used in EOM calculations. TYPE: LOGICAL DEFAULT: FALSE OPTIONS: TRUE Solve for a state that has maximum overlap with a trans-n specified in$eom_user_guess.
RECOMMENDATION:
The orbitals are ordered by energy, as printed in the beginning of the CCMAN2 output. Not available in CCMAN.

EOM_SHIFT

EOM_SHIFT
Specifies energy shift in EOM calculations.
TYPE:
INTEGER
DEFAULT:
0
OPTIONS:
$n$ corresponds to $n\cdot 10^{-3}$ hartree shift (i.e., 11000 = 11 hartree); solve for eigenstates around this value.
RECOMMENDATION:
Not available in CCMAN.

EOM_NGUESS_DOUBLES

EOM_NGUESS_DOUBLES
Specifies number of excited state guess vectors which are double excitations.
TYPE:
INTEGER
DEFAULT:
0
OPTIONS:
$n$ Include $n$ guess vectors that are double excitations
RECOMMENDATION:
This should be set to the expected number of doubly excited states, otherwise they may not be found.

EOM_NGUESS_SINGLES

EOM_NGUESS_SINGLES
Specifies number of excited state guess vectors that are single excitations.
TYPE:
INTEGER
DEFAULT:
Equal to the number of excited states requested
OPTIONS:
$n$ Include $n$ guess vectors that are single excitations
RECOMMENDATION:
Should be greater or equal than the number of excited states requested, unless .

EOM_PRECONV_SINGLES

EOM_PRECONV_SINGLES
When not zero, singly excited vectors are converged prior to a full excited states calculation. Sets the maximum number of iterations for pre-converging procedure.
TYPE:
INTEGER
DEFAULT:
0
OPTIONS:
0 do not pre-converge 1 pre-converge singles
RECOMMENDATION:
Sometimes helps with problematic convergence.

Note:  In CCMAN, setting EOM_PRECONV_SINGLES = $N$ would result in $N$ Davidson iterations pre-converging singles.

EOM_PRECONV_DOUBLES

EOM_PRECONV_DOUBLES
When not zero, doubly excited vectors are converged prior to a full excited states calculation. Sets the maximum number of iterations for pre-converging procedure
TYPE:
INTEGER
DEFAULT:
0
OPTIONS:
0 Do not pre-converge N Perform N Davidson iterations pre-converging doubles.
RECOMMENDATION:
Occasionally necessary to ensure a doubly excited state is found. Also used in DSF, DIP, and DEA calculations instead of EOM_PRECONV_SINGLES

Note:  Not available for EOM-EE in CCMAN2.

EOM_PRECONV_SD

EOM_PRECONV_SD
When not zero, EOM vectors are pre-converged prior to a full excited states calculation. Sets the maximum number of iterations for pre-converging procedure.
TYPE:
INTEGER
DEFAULT:
0
OPTIONS:
0 do not pre-converge N perform N Davidson iterations pre-converging singles and doubles.
RECOMMENDATION:
Occasionally necessary to ensure that all low-lying states are found. Also, very useful in EOM(2,3) calculations.

None

Note:  Not available in CCMAN2.

EOM_DAVIDSON_CONVERGENCE

EOM_DAVIDSON_CONVERGENCE
Convergence criterion for the RMS residuals of excited state vectors.
TYPE:
INTEGER
DEFAULT:
5 Corresponding to $10^{-5}$
OPTIONS:
$n$ Corresponding to $10^{-n}$ convergence criterion
RECOMMENDATION:
Use the default. Normally this value be the same as EOM_DAVIDSON_THRESHOLD.

EOM_DAVIDSON_THRESHOLD

EOM_DAVIDSON_THRESHOLD
Specifies threshold for including a new expansion vector in the iterative Davidson diagonalization. Their norm must be above this threshold.
TYPE:
INTEGER
DEFAULT:
00103 Corresponding to 0.00001
OPTIONS:
$abcde$ Integer code is mapped to $abc\times 10^{-(de+2)}$, i.e., 02505->2.5$\times 10^{-6}$
RECOMMENDATION:
Use the default unless converge problems are encountered. Should normally be set to the same values as EOM_DAVIDSON_CONVERGENCE, if convergence problems arise try setting to a value slightly larger than EOM_DAVIDSON_CONVERGENCE.

EOM_DAVIDSON_MAXVECTORS

EOM_DAVIDSON_MAXVECTORS
Specifies maximum number of vectors in the subspace for the Davidson diagonalization.
TYPE:
INTEGER
DEFAULT:
60
OPTIONS:
$n$ Up to $n$ vectors per root before the subspace is reset
RECOMMENDATION:
Larger values increase disk storage but accelerate and stabilize convergence.

EOM_DAVIDSON_MAX_ITER

EOM_DAVIDSON_MAX_ITER
Maximum number of iteration allowed for Davidson diagonalization procedure.
TYPE:
INTEGER
DEFAULT:
30
OPTIONS:
$n$ User-defined number of iterations
RECOMMENDATION:
Default is usually sufficient

EOM_IPEA_FILTER

EOM_IPEA_FILTER
If TRUE, filters the EOM-IP/EA amplitudes obtained using the diffuse orbital implementation (see EOM_FAKE_IPEA). Helps with convergence.
TYPE:
LOGICAL
DEFAULT:
FALSE (EOM-IP or EOM-EA amplitudes will not be filtered)
OPTIONS:
FALSE, TRUE
RECOMMENDATION:
None

Note:  Not available in CCMAN2.

CC_FNO_THRESH

CC_FNO_THRESH
Initialize the FNO truncation and sets the threshold to be used for both cutoffs (OCCT and POVO).
TYPE:
INTEGER
DEFAULT:
None
OPTIONS:
range 0000-10000 $abcd$ Corresponding to $ab.cd$%
RECOMMENDATION:
None

CC_FNO_USEPOP

CC_FNO_USEPOP
Selection of the truncation scheme.
TYPE:
INTEGER
DEFAULT:
1 OCCT
OPTIONS:
0 POVO
RECOMMENDATION:
None

SCALE_NUCLEAR_CHARGE

SCALE_NUCLEAR_CHARGE
Scales charge of each nuclei by a certain value. The nuclear repulsion energy is calculated for the unscaled nuclear charges.
TYPE:
INTEGER
DEFAULT:
0 No scaling.
OPTIONS:
$n$ A total positive charge of (1+$n/100$)e is added to the molecule.
RECOMMENDATION:
NONE

Add a point charge cage of a given radius and total charge.
TYPE:
INTEGER
DEFAULT:
0 No cage.
OPTIONS:
0 No cage. 1 Dodecahedral cage. 2 Spherical cage.
RECOMMENDATION:
Spherical cage is expected to yield more accurate results, especially for small radii.

Defines radius of the charged cage.
TYPE:
INTEGER
DEFAULT:
225
OPTIONS:
$n$ radius is $n/100$ Å.
RECOMMENDATION:
None

CAGE_POINTS

CAGE_POINTS
Defines number of point charges for the spherical cage.
TYPE:
INTEGER
DEFAULT:
100
OPTIONS:
$n$ Number of point charges to use.
RECOMMENDATION:
None

CAGE_CHARGE

CAGE_CHARGE
Defines the total charge of the cage.
TYPE:
INTEGER
DEFAULT:
400 Add a cage charged +4e.
OPTIONS:
$n$ Total charge of the cage is $n/100$ a.u.
RECOMMENDATION:
None