12 Fragment-Based Methods

12.17 Ab Initio Frenkel Davydov Exciton Model (AIFDEM)

(May 16, 2021)

The Frenkel-Davydov Exciton model is an old idea for describing the (potentially delocalized) excited states of molecular crystals, or more generally noncovalent assemblies or aggregates of weakly electronically-coupled chromophores, as linear combinations of fragment-localized excited states. The Ith collective excited state, |ΞI, is thus written

|ΞI=nsitesistatesKnIi|Ψnimn|Ψm, (12.67)

where |Ψni is the ith excited state of the nth molecular fragment and |Ψm is the ground-state wave function of the mth fragment. Eigenstates and energies are found by constructing and diagonalizing the electronic Hamiltonian matrix in this direct product, “exciton-site” basis.

In the ab initio Frenkel-Davydov exciton model (AIFDEM) developed by Morrison and Herbert, 774 Morrison A. F., You Z.-Q., Herbert J. M.
J. Chem. Theory Comput.
(2014), 10, pp. 5366.
Link
, 771 Morrison A. F., Herbert J. M.
J. Phys. Chem. Lett.
(2015), 6, pp. 4390.
Link
, 772 Morrison A. F., Herbert J. M.
J. Phys. Chem. Lett.
(2017), 8, pp. 1442.
Link
, 773 Morrison A. F., Herbert J. M.
J. Chem. Phys.
(2017), 146, pp. 224110.
Link
the ground-state wave functions in Eq. (12.67) are single Slater determinants (obtained from SCF calculations on isolated fragments), and the fragment excited-state wave functions are linear combinations of singly-excited determinants:

|ΨA=iaCia|ΦAia. (12.68)

The AIFDEM approach computes elements of the exact Hamiltonian,

ΨAΨBΨC|H^|ΨAΨBΨC=iaσkbτCσiaCτkbΦAiaΦBΦC|H^|ΦAΦBkbΦC. (12.69)

In particular, no dipole-coupling approximation is made (as is often invoked in simple exciton models). Such an approximation may be valid for well-separated chromophores but likely less so for tightly-packed chromophores in a molecular crystal. Overlap matrices

ΨAΨBΨC|ΨAΨBΨC=iaσkbτCσiaCτkbΦAiaΦBΦC|ΦAΦBkbΦC (12.70)

are also required because molecular orbitals located on different fragments are not orthogonal to one another. In order to reduce the number of terms in Eqs. (12.69) and (12.70), the fragment excited states are transformed into the natural transition orbital (NTO) basis (see Section 7.14.2) and then the corresponding orbitals transformation (Section 10.15.2.2) is used to compute matrix elements between non-orthogonal Slater determinants. The size of the exciton-site basis is sufficiently small such that eigenvectors and energies of the exciton Hamiltonian can be printed and saved to scratch files. Transition dipole moments between the ground state and the first ten excited states of the exciton Hamiltonian are also computed.

The cost to compute each matrix element scales with the size of the supersystem (somewhere between quadratic and quartic with monomer size), since all fragments must be included in the direct products. To reduce this scaling, a physically-motivated charge embedding scheme was introduced 771 Morrison A. F., Herbert J. M.
J. Phys. Chem. Lett.
(2015), 6, pp. 4390.
Link
that only treats the excited fragments, and neighbors within a user-specified distance threshold, with full QM calculation, while the other ground state fragment interactions are approximated by atomic point charges. In general, inclusion of neighboring fragments in the QM part of the matrix element evaluation does not seem to significantly improve the accuracy and diminishes the cost savings of the charge-embedding procedure. Therefore, the minimal “0 Å” threshold, where only the excited fragments are described at a QM level, can be considered optimal. Charge embedding with the minimal threshold affords an algorithm that scales as NF2×𝒪(npair2-4), where NF is the number of fragments and npair is the size of a pair of fragments.

The exciton-site basis can be expanded to include higher-lying fragment excited states which affords the wave function increased variational flexibility, and can significantly improve the accuracy for polar systems and delocalized excited states. The number of fragment excited states included in the basis is specified by the CIS_N_ROOTS keyword, which must be 1. A cost effective means of including polarization effects is to use the XPol method to compute fragment ground state, and the nature of the atomic point charges is therefore controlled by keywords specified in the $xpol input section, as described in Section 12.12. Fragment excited states are then computed using the XPol-polarized MOs. Two additional types of states can be included in the AIFDEM basis. These may be of the charge transfer-type,where the states are of the form |ΦA+ΦB-ΦC, where ΦA± are cationic or anionic determinants from unrestricted SCF calculations on the isolated fragments. “Multi-exciton” states, of the type |1(ΦATΦBT)ΦC, are also easily included in the basis. These states couple triplet wave functions on two different monomers to an overall singlet, and have been used to study the singlet fission process in tetracene and pentacene. 772 Morrison A. F., Herbert J. M.
J. Phys. Chem. Lett.
(2017), 8, pp. 1442.
Link
, 32 Alam B., Morrison A. F., Herbert J. M.
J. Phys. Chem. C
(2020), 124, pp. 24653.
Link

The exciton-site basis states are spin-adapted to form proper S^2 eigenstates.Their multiplicity determines that of the target excited state and this must be specified by setting CIS_SINGLETS or CIS_TRIPLETS to TRUE. The number of terms included in Eqs. (12.69) and (12.70) can be rationally truncated at some fraction of the norm of the fragment NTO amplitudes, in order to reduce cost at the expense of accuracy, although the approximation is controllable by means of the truncation threshold. Computation time scales approximately quadratically with the number of terms and a threshold of about 85% has been found to maintain acceptable accuracy for organic molecules with reasonable cost. The fragment orbitals and excited states may be computed with any SCF and single-excitation theory, including DFT and TDDFT, however the coupling matrix elements are always computed with a CIS-like Hamiltonian with no DFT exchange-correlation. Both OpenMP and MPI parallel implementations are available; the former distributes two-electron integral computation across cores in a node as in a traditional excited-state calculation, the latter can distribute matrix element evaluations across hundreds of cores with minimal overhead.

There are many chemical processes of interest where motion of nuclei induces electronic transitions, in a breakdown of the Born-Oppenheimer approximation. In order to investigate such processes it is useful to calculate some quantity that codifies the coupling of adiabatic electronic states dues to nuclear motion. In molecular electronic structure theory this quantity is the nonadiabatic coupling (or “derivative coupling”) vector ΨI|(/x)|ΨJ, which describes how the nuclear position derivative /x couples adiabatic (Born-Oppenheimer) electronic states ΨI and ΨJ. In solid-state physics these ideas are typically not discussed in terms of the Born-Oppenheimer approximation but rather in terms of the so-called “Holstein” and “Peierls” exciton/phonon coupling constants (see below). Within the framework of the AIFDEM, each of these quantities can be computed from a common intermediate 𝐇[x], which is the derivative of the AIFDEM Hamiltonian matrix with respect to some nuclear coordinate x. 772 Morrison A. F., Herbert J. M.
J. Phys. Chem. Lett.
(2017), 8, pp. 1442.
Link
, 773 Morrison A. F., Herbert J. M.
J. Chem. Phys.
(2017), 146, pp. 224110.
Link
Diagonal matrix elements HAA[x]HAA/x describe how the exciton-site energies are modulated by nuclear motion and off-diagonal matrix elements HAB[x]HAB/x describe how nuclear motion modifies the energy-transfer couplings.

Once 𝐇[x] has been constructed, then the nonadiabatic coupling vector between eigenstates ΨI and ΨJ of the exciton Hamiltonian is simply

𝐡IJ=𝐊I𝐇[x]𝐊J. (12.71)

The Holstein (A=B) and Peierls (AB) coupling constants gABθ, expressed in dimensionless normal mode coordinates, are 773 Morrison A. F., Herbert J. M.
J. Chem. Phys.
(2017), 146, pp. 224110.
Link

gABθ=(2μθωθ)-1/2xH~AB[x]Lxθ (12.72)

where the matrix 𝐋 is the transformation between Cartesians coordinates and normal (phonon) modes. The columns of 𝐋 contain the normalized Cartesian displacements of normal mode θ, whose frequency and effective mass are ωθ and μθ, respectively. The tilde on, H~AB[x] indicates that the matrix element derivatives have been orthogonalized (including the derivative of the orthogonalization transformation). 773 Morrison A. F., Herbert J. M.
J. Chem. Phys.
(2017), 146, pp. 224110.
Link

A basic AIFDEM calculation is requested by setting AIFDEM = TRUE in the $rem section, with additional job-control variables as described below.

AIFDEM
       Perform an AIFDEM calculation.
TYPE:
       LOGICAL
DEFAULT:
       FALSE
OPTIONS:
       FALSE Do not perform an AIFDEM calculation. TRUE Perform an AIFDEM calculation.
RECOMMENDATION:
       False

AIFDEM_NTOTHRESH
       Controls the number of NTOs that are retained in the exciton-site basis states.
TYPE:
       INTEGER
DEFAULT:
       99
OPTIONS:
       n Threshold percentage of the norm of fragment NTO amplitudes.
RECOMMENDATION:
       A threshold of 85% gives a good trade-off of computational time and accuracy for organic molecules.

AIFDEM_EMBED_RANGE
       Specifies the size of the QM region for charge embedding
TYPE:
       INTEGER
DEFAULT:
       FULL_QM
OPTIONS:
       FULL_QM No charge embedding. 0 Treat only excited fragments with QM. n Range (in Å) from excited fragments within which to treat other fragments with QM.
RECOMMENDATION:
       The minimal threshold of zero Å typically maintains accuracy while significantly reducing computational time.

AIFDEM_CTSTATES
       Include charge-transfer-like cation/anion pair states in the AIFDEM basis.
TYPE:
       LOGICAL
DEFAULT:
       FALSE
OPTIONS:
       TRUE Include CT states. FALSE Do not include CT states.
RECOMMENDATION:
       None

AIFDEM_SINGFIS
       Include multiexciton states in the AIFDEM basis.
TYPE:
       LOGICAL
DEFAULT:
       FALSE
OPTIONS:
       TRUE Include multiexciton states. FALSE Do not include multiexciton states.
RECOMMENDATION:
       None

For calculations on large systems, it may be desirable to break up the calculation of the AIFDEM matrix elements into batches. The user can specify can specify the first and last matrix element for a calculation with the following variables.

AIFDEM_SEGSTART
       Indicates the index of the first matrix element to be computed.
TYPE:
       INTEGER
DEFAULT:
       NONE
OPTIONS:
       n First matrix element of chunk to be computed.
RECOMMENDATION:
       Needs to be used with AIFDEM_SEGEND

AIFDEM_SEGEND
       Indicates the index of the last matrix element to be computed.
TYPE:
       INTEGER
DEFAULT:
       NONE
OPTIONS:
       n Last matrix element of chunk to be computed.
RECOMMENDATION:
       Needs to be used with AIFDEM_SEGSTART

When computing AIFDEM matrix elements in batches, one can avoid running fragment scf calculations for each job, by first running a job that runs only the fragment SCF calculations. These are saved in the scratch directory. These may then be read into subsequent calculations. The following variables control this utility.

AIFDEM_FRGM_WRITE
       Fragment SCF calculations only.
TYPE:
       LOGICAL
DEFAULT:
       FALSE
OPTIONS:
       TRUE Only fragment scf calculations are carried out, no computation of matrix elements. FALSE Regular AIFDEM calculation as specified by other REM variables.
RECOMMENDATION:
       None

AIFDEM_FRGM_READ
       Skips fragment scf calculations.
TYPE:
       LOGICAL
DEFAULT:
       FALSE
OPTIONS:
       TRUE Skips fragment scf calculations, only computation of matrix elements. FALSE Regular AIFDEM calculation as specified by other REM variables.
RECOMMENDATION:
       Requires a prior calculation that computes fragment scf data.

For charge-embedded AIFDEM calculations, set XPOL = TRUE in the $rem section and then select the type of embedding charges via the $xpol input section, as described in Section 12.12 and illustrated in the following example.

Example 12.41  Example showing singlet excited state calculation, on (H2O)4. XPol is used to generate monomer wave functions with ChElPG charges. Minimal QM charge embedding is used for the exciton model with three excited states per fragment.

$molecule
0 1
--H2O 0
   0 1
   O          1.74078        1.59716       -1.49814
   H          2.22908        2.18316       -2.08914
   H          0.88038        2.04726       -1.32684
--H2O 1
   0 1
   O          1.31998       -1.18934       -1.91734
   H          1.49988       -0.22974       -1.89044
   H          1.69058       -1.52594       -1.07704
--H2O 2
   0 1
   O         -0.68982        2.59476       -0.72224
   H         -1.14372        3.37086       -1.07364
   H         -1.35592        1.84986       -0.78334
--H2O 3
   0 1
   O         -1.27512       -1.77394       -1.69524
   H         -0.32252       -1.52884       -1.85604
   H         -1.53992       -2.30454       -2.45644
$end

$rem
   BASIS                aug-cc-pvdz
   EXCHANGE             HF
   CIS_N_ROOTS          3
   CIS_TRIPLETS         FALSE
   XPOL                 TRUE
   AIFDEM               TRUE
   AIFDEM_EMBED_RANGE   0
   AIFDEM_NTOTHRESH     90
   NTO_PAIRS            1
$end

$xpol
  embed   charges
  charges CHELPG
$end

View output

To compute AIFDEM derivatives 𝐇[x] and 𝐒[x] of the Hamiltonian and overlap matrices, the user should request a standard AIFDEM job and in addition set CIS_STATE_DERIV = 1. Currently, the AIFDEM derivatives do not support charge embedding so the keyword AIFDEM_EMBED_RANGE must be omitted from these jobs, which precludes the use of XPol wavefunctions for the fragments. Furthermore, only one excited state per fragment is supported so the keyword CIS_N_ROOTS = 1. is required.

The derivatives of the AIFDEM Hamiltonian matrix and overlap matrix are printed in the output file in sets of the three Cartesian coordinates that belong to a single atom. For convenience, the orthogonalized AIFDEM Hamiltonian matrix elements are saved in the scratch directory, $QCSCRATCH/aifdem_deriv. These are organized such that the derivatives for each unique matrix element are stored in individual files in the order of the atomic Cartesian coordinates. These files can facilitate external calculation of exciton/phonon coupling constants.

Example 12.42  A basic AIFDEM derivative calculation on a chain of helium atoms.

$molecule
0 1
--frgm 0
0 1
He    0.000   0.000   0.000
He    0.000   0.000   1.400
--frgm 1
0 1
He    0.000   0.000   2.800
He    0.000   0.000   4.200
$end

$rem
   BASIS             =  cc-pvdz
   EXCHANGE          =  hf
   AIFDEM            =  true
   CIS_N_ROOTS       =  1
   CIS_SINGLETS      =  true
   CIS_TRIPLETS      =  false
   CIS_STATE_DERIV   =  1
   NTO_PAIRS         =  1
   MEM_TOTAL         =  1000
   MEM_STATIC        =  1000
   MAX_CIS_CYCLES    =  200
   MAX_SCF_CYCLES    =  200
   THRESH            =  10
   AIFDEM_NTOTHRESH  =  100
$end

View output