Corrected Linear Response
State-specific correction to solvent polarization response
March 2016
Ciro Guido 1 & Stefano Caprasecca2
An online version of this guide may be found on
[Link]/molecolab/tools/white-papers/pisalr
These notes explain the correct procedure to obtain excitation energies (both
absorption and emission) in solution by using the state-specific corrected linear
response (cLR) approach of Caricato et al., 1 as developed in this group some time
ago.
The method is already available in the G09 version of the Gaussian suite of
programs. 2 The importance of such kind of simulations is due to the fact that, for
excitations involving a large density rearrangement, the Linear Response scheme is
insufficient 3 because it does not account for the density-dependent relaxation of
the solvent polarization.
Please note that this is here explained for a continuum solvent described with the
Polarizable Continuum Model. 4 It can however be used also with other polarizable
models for the environment, such as the polarizable MM (MMPol) developed in this
group. 5
A summary of the theory is briefly detailed below. For further details, we refer
to Refs. 1,3,6,7
A step-by-step guide on the usage in Gaussian follows.
Usage in Gaussian
1. Geometry optimizationof the ground state
Start by optimizing the ground state structure and calculating the frequencies, in
the presence of the solvent:
1 [Link]@[Link]
2 [Link]@[Link]
1
Figure 1: Schematic illustration of the steps described below, necessary to compute
absorption and fluorescence.
#p B3LYP/6-311G(d) SCRF=(IEFPCM,SOLVENT=ACETONITRILE) OPT FREQ
2. Vertical excitation (absorption)
The absorption calculation consists in a TD single-point excitation from the optim-
ized ground state geometry in the presence of the solvent:
#p CAM-B3LYP/6-311G(d) SCRF=(PISALR,SOLVENT=ACETONITRILE)
TD=(NSTATES=5,ROOT=1,NONEQ) IOP(10/74=10)
Here we have specified:
(a) to use the cLR approach (PISALR);
(b) the state of interest (e.g., ROOT=1);
(c) that it is a non-equilibrium solvation (NONEQ). This indicates that we are con-
sidering a vertical process, where the dynamical response of the solvent imme-
diately equilibrates with the excited state density, while the inertial part is not
in equilibrium with it, and remains in equilibrium with the ground state;
(d) the extra input (IOP(10/74=10)) is needed when cLR is used with non-equilibrium
solvation. Please note that, being a state-specific approach, the calculation
2
should be repeated for each state you are interested in, changing the state of
interest.
In the output, apart from the standard LR results, the cLR energies will appear
as follows:
PCM Corrected Linear-Response - Non-equilibrium solvation:
Corrected transition energy = 4.6316 eV
Total energy after correction = -192.868770368 a.u.
The absorption energy thus is 4.63 eV.
3. Geometry optimization of the excited state
As for step (1), a geometry optimization for the excited state of interest (here, state
1) is needed:
#p CAM-B3LYP/6-311G(d) SCRF=(IEFPCM,SOLVENT=ACETONITRILE)
TD(NSTATES=5,ROOT=1,EQSOLV) OPT FREQ=NUM
Where:
(a) specifying the OPT keyword when TD is active, and a certain state is selected,
means that the geometry optimization refers to that particular excited state;
(b) the keyword EQSOLV specifies that the solvent is now in equilibrium with the
excited state;
(c) analytical frequencies are only available for the ground state. If they need to
be computed for the excited state, numerical ones (much slower) must be used
instead (FREQ=NUM)
4. Determination of the reaction field of the excited state
Once the excited state structure is optimized, the emission simulation requires a
two-step calculation (here, steps 4 and 5). The two steps can be executed at once
with one input file.
In step 4, the inertial part of the reaction field due to the excited state is
determined. This needs to be saved and then used, in the second calculation, for
the final emission.
(a) In TD, it is specified that the solvation is in equilibrium with the excited state
(EQSOLV);
(b) in the SCRF keywords, READ specifies that, at the end of the input section, extra
keywords need to be read;
(c) the extra keywords are written after the molecular structure. NONEQ=SAVE
specifies that the inertial part of the solvation needs to be saved, to be used
again in the following calculation;
(d) note that the checkpoint [Link] will contain all such information and will
have to be read in the next step (5).
3
5. Vertical de-excitation (emission)
In this step, the inertial reaction field is read (NONEQ=LOAD). Both the geometry and
the guess for the electron density are read from the previous checkpoint (GUESS=READ,
GEOM=CHECKPOINT)
The following input file includes both steps 4 and 5.
%chk=[Link]
#p CAM-B3LYP/6-311G(d) TD(NSTATES=5,ROOT=1,EQSOLV)
SCRF=(PISALR,SOLVENT=ACETONITRILE,READ) IOp(10/74=20)
TITLE SECTION: EMISSION FROM S1 IN ACN, STEP 4
[charge] [multiplicity]
[geometry]
NONEQ = SAVE
-- Link1 --
%oldchk=[Link]
%chk=[Link]
#p CAM-B3LYP/6-311G(d) GUESS=READ GEOM=CHECKPOINT
SCRF(SOLVENT=ACETONITRILE,READ)
TITLE SECTION: EMISSION FROM S1 IN ACN, STEP 5
[charge] [multiplicity]
NONEQ=LOAD NONEQPARTITION=DYNAMICINERTIAL
The de-excitation energy can now be calculated in the following way:
(a) take the total energy after correction:
PCM State-Specific 1st Order Perturbation Theory - Equilibrium solvation.
Corrected transition energy = 2.5307 eV
Total energy after correction = -1032.54876403 a.u.
(b) compare it with the ground state energy of the last calculation, i.e., step 5:
SCF Done: E(RCAM-B3LYP) = -1032.64119112 A.U. after 11 cycles
(c) the difference yields the corrected de-excitation energy in Hartree, which can
be converted to eV:
−1032.54876403 a.u. − (−1032.64119112texta.u.) = 0.0924271 a.u.
0.0924271 a.u. · 27.211399 eV/a.u. = 2.5151 eV
Theory overview
During the past decade, two principal formulations have been proposed and tested
to couple the solute QM description with continuum models when describing the
environment response following a vertical excitation/de-excitation. The two ap-
proaches, called Linear Response (LR) and State-specific (SS) models, respectively,
can be illustrated by ideally reformulating the excitation in solution as a two-step
process: first, the molecule, in its ground state, in equilibrium with the solvent,
4
is excited to an excited state i in the presence of a solvent polarization frozen to
0
the initial ground state (ω0i ). In the second step, the dynamic component of the
solvent polarization rearranges to equilibrate with the excite state charge density of
the solute.
Based on the Rayleigh-Schrödinger perturbation theory, Cammi et al. 7 derived
comparable expressions for both frameworks, namely:
D E
0
LR
ω0i = ω0i + i (0) V̂ |0i h0| Q̂dyn i (0) = ω0i0
+ RdynLR
(P0iT )
0 1 hD (0) (0) E i hD E i
SS
ω0i = ω0i + i V̂ i − h0| V̂ |0i i (0) Q̂dyn i (0) − h0| Q̂dyn |0i
2
0 SS
= ω0i + Rdyn (P0i∆ )
where V̂ is the molecular electrostatic
potential operator, Q̂dyn is the dynamical
apparent charge operator. i (0) is the i-th electronic state obtained in the presence
of the fixed reaction field due to the ground state |0i. Note that this is just an
explanatory picture, which does not correspond to the actual implementation.
In the LR formulation, the response Rdyn of the solvent dynamic polarization to
the excitation is computed from the transition density (P0iT ), while in the SS ap-
proach the same polarization is determined by the difference of the electron densities
of the initial and final states, (P0i∆ ).
The LR formulation is generally well-suited for transitions characterized by a
small change of the electron density, since the electrostatic interaction between the
solvent and the excited state density is not very different from that of the ground
state. By contrast, for excitations involving a large density rearrangement, the
LR scheme is insufficient because the density-dependent relaxation of the solvent
polarization is not included. In those cases, the difference between LR and SS
schemes can therefore become significant. 3
In the framework of TDDFT and CIS electronic structure methods, different
state-specific formulations of TD with PCM have been suggested: the corrected
linear response (cLR, also known as PisaLR 1 ), and its self-consistent and variational
generalization: the Vertical Excitation Method (VEM 6 ). The cLR can be considered
as the first cycle of the iterative process of VEM.
5
Bibliography
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G. Scalmani, J. Chem. Phys., 2006, 124, 124520.
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