CONTINUUM SOLVATION MODELS IN

GAUSSIAN 03
Dr. Ivan Rostov
Australian National University,
Canberra
E-mail: Ivan.Rostov@anu.edu.au
OUTLINE
Types of solvent effects and solvent models
Overview of solvation continuum models
available in Gaussian 03.
Summary of Gaussian keywords
Applications
Recommendations

2
SOLVENT EFFECTS
3
Nicolai Alexandrovich Menshutkin, Z. Physik. Chem. 1890, 5, 589
NH
3
CH
3
Cl NH
3
CH
3
+

Cl

SOLVENT EFFECTS
The solvent environment influences all of
these:
Structure
Energies
Reaction and activation energies
Bond energies
Spectra
Rotational (Microwave)
Vibrational (IR, Raman)
Electronic (UV, visible)

4
METHODS FOR TREATMENT OF
SOLVATION
Supermolecule
Solute and some number of solvent molecules are included in one
large QM calculation
Molecular Mechanics Force Fields
Simple classical force fields allows us to include a large number of
solvent molecules
Continuum models
Explicit consideration of solvent molecules is neglected
Solvent effects are described in terms of macroscopic properties of
the chosen solvent (c, <Rsolvent>)
Hybrid/mixed:
Supermolecule + Continuum model
QM + MM
QM + MM + Continuum model
5
6
SOLVATION PROCESS
. . . elec rep disp cav solv
U U U U + + =

1) Creation of cavity 3) Turning on

electrostatic forces
elec rep. - disp.
iN iN
F F

+
2) Turning on
dispersion and
repulsion forces
rep. - disp.
iN
F

BASICS OF THE CONTINUUM MODEL

THEORY
Solvent is described in terms of macroscopic
properties
Solvent is dielectric medium (uniform, normally),
characterized by the dielectric constant c
0
Polarization of solvent is expressed in terms of the
surface charge density on the cavity surface
Polarization produces the electric field in the cavity
making an effect on solute
Dispersion-Repulsion and Cavitation are added
separately, or ignored
7
8
THE ELECTROSTATIC PROBLEM
c c = 1 = 1
c c = = c c
0 0
S S
c c = 1 = 1
c c = = c c
0 0
S S
Solution is calculated as
r r
r
r
r r
r
r r
'

'
'
+
'

'
'
=
} }
) ( ) (
) (
2 3
o

S V
d d

= V
0
4
2
t

( )
( )
e
i
V
V
e
e
r
r
Poisson equations
with boundary conditions
on S:
n n c
c
=
c
c
=
out in
out in

BORN MODEL
9
A single charge inside a spherical cavity
No constructing of the cavity surface elements, because
the Poisson equation is solved analytically
R
Q
U
solv
2
0
1
1
|
|
.
|

\
|
=
c
ONSAGER MODEL
Spherical cavity
Dipolar reaction field
No constructing of the cavity surface elements, because
the Poisson equation is solved analytically
Keywords in Gaussian:
SCRF(Dipole,A0=value,Dielectric=value)
Area of applicability:
Solute shape is close to spherical
Solute is polar ( >> 0)
References
L. Onsager, J. Am. Chem. Soc. 58, 1486 (1936).
M. Wong, M. Frisch, K. Wiberg, J. Am. Chem. Soc. 113, 4476
(1991).
+
+

+ =
1 2
1
0
0
3
2
c
c
R
H E

10
POLARIZED CONTINUUM MODEL (PCM)
Realistic molecular shape of the cavity (interlocking spheres
around each atom or group, or isodensity surface)
Induced surface charges represent solvent polarization
Includes free energy contributions from forming the cavity
and dispersion-repulsion
Comes in number of flavours:
IEFPCM, CPCM, DPCM, IPCM, or SCIPCM
Keywords in Gaussian:
SCRF(Solvent=, PCM specific options)
References:
E. Canses, B. Mennucci, J. Tomasi, J. Chem Phys. 107, 3032 (1997).
J. Tomasi, M. Persico, Chem. Rev. 94,2027 (1994).
J. Tomasi, B. Mennucci, R. Camm, Chem. Rev. 105, 2999 (2005).
11
PCM, THE CAVITY CONSTRUCTION
Interlocking spheres around atomic groups
This is default in Gaussian 03
A choice of united atoms radii set, RADII=UAO (default), UAHF, UAKS,
or UFF
Interlocking spheres around each atom
Radii=Pauling (or Bondi)
Requires the scaling factor ALPHA by which the sphere radius is
multiplied. The default value is 1.0 though should be 1.2
A number of keywords is provided to add extraspheres when
necessary
A number of keyword is provided to govern the size and
number of surface elements (tesserae)
12
PCM, THE CAVITY VIEW
Keyword: GeomView
Creates files in GeomView format to visualize the cavity
construction and the charge distribution on the cavity:
tesserae.off
charge.off
Files are readable by GeomView, JavaView and other visualization software.
13
(C
5
NH
12
+
)
PCM, METHODS OF SOLVING OF THE SCRF
PROBLEM TO CALCULATE SURFACE CHARGES
Iterative
Keyword: ITERATIVE
Solves the PCM electrostatic problem
through a linear scaling iterative
method using a Jacobi-like scheme
Advantageous when memory is
limited.
Inversion
Keyword: INVERSION
Solve the PCM electrostatic problem to
calculate polarization charges through
the inversion matrix D with dimension
of N
tes
xN
tes
Gaussian 03 uses Inversion by default.
( ) ( ) ( ) ( )
(
(

+ '
'
' + '
'
' =
} }
r r
r r r
r r
r r r
r r to o
c
c

c
c
o 2
1
) (
1
) (
1
2 3
0 S V
n
d
n
d
f
( )
i
i
S
q
A
A
r o
14
( ) ) ( ) (

) ' (

1
r r' r, r r, r o V D

=
DIELECTRIC PCM
The original version of PCM
Electrostatics directly from the cavity model
Charges produces by discontinuity in the electric field
across the boundary created by the cavity
Very sensitive to solute charge outside the cavity
Only single point calculations
No longer recommended

15
INTEGRAL EQUATION FORMALISM PCM
(IEFPCM)
Default in Gaussian 03
Less sensitive to diffuse solute charge
distributions
PCM + careful outlying charge corrections =>
IEFPCM
16
CPCM (COSMO)
Uses the assumption that the cavity surface to be
conductor-like
This assumption simplifies the solution of Poisson
equation and calculation of the surface charges
Results can be outputted in COSMO RS format
Not recommended for solvents with low polarity
It is more efficient in iterative regime
17
ISODENSITY PCM (IPCM) AND
SELF-CONSISTENT ISODENSITY PCM (SCIPCM)
Cavity formed using gas-phase static electronic isodensity
surface (IPCM)
Less arbitrary than spheres on atoms
Cavity changes with electron density and environment
The default density value is 0.0004
only single point calculations
Self-Consistent Isodensity (SCIPCM)
iterations are folded in SCF
issues regarding scaling of charges still remain
References
J. Foresman, T.Keith, K. Wiberg, J. Snoonian, M. Frisch,
J. Phys. Chem. 100,16098 (1996).
18
GAUSSIAN 03 KEYWORD EXAMPLES
19
SCRF(Dipole,A0=5.5,eps=78.39)

SCRF(IEFPCM) is the same as SCRF(PCM), or just SCRF

SCRF(CPCM,Solvent=THF,Read)

SCRF(IPCM)

SCRF(SCIPCM)
SAMPLE INPUT FOR PCM CALCULATIONS
20
%chk=pip-pcm
#P HF/6-31g(d) SCRF(PCM,Solvent=Water,Read) test

Piperidinium cation

1 1
N
C 1 1.50977268
C 2 1.52365511 1 109.63925419
C 3 1.53136665 2 111.56508108 1 -55.04631728
C 1 1.50978576 2 113.42079276 3 57.07092348
C 4 1.53134037 3 110.99585756 2 54.90811126
H 1 1.00969298 5 109.64667654 6 -179.99768911
H 1 1.01028619 5 109.06107319 6 64.67690355
H 2 1.08151743 1 106.09798567 5 -64.03241054
H 2 1.08069845 1 107.09512052 5 179.68520816
H 3 1.08732966 2 109.45874935 1 67.33780856
H 3 1.08342937 2 107.81444282 1 -177.04873713
H 4 1.08661607 3 109.70973952 2 -66.50424273
H 4 1.08269752 3 109.4557835 2 176.38517116
H 5 1.08069728 1 107.09836585 2 -179.68240007
H 5 1.08151732 1 106.09918524 2 64.03563496
H 6 1.08732304 4 110.31444998 3 66.98445589
H 6 1.08344075 4 110.90163383 3 -175.10999479

PCMDOC
ITERATIVE
GEOMVIEW
PCM solvation is
requested. Solvent is
Water. Additional PCM
specific keywords are
provided
PCM specific keywords
SAMPLE OUTPUT
21
SCF Done: E(RHF) = -250.669391936 A.U. after 6 cycles
Convg = 0.7269D-05 -V/T = 2.0012
S**2 = 0.0000
--------------------------------------------------------------
Variational PCM results
=======================
<psi(f)| H |psi(f)> (a.u.) = -250.570493
<psi(f)|H+V(f)/2|psi(f)> (a.u.) = -250.669392
Total free energy in solution:
with all non electrostatic terms (a.u.) = -250.662541
--------------------------------------------------------------
(Polarized solute)-Solvent (kcal/mol) = -62.06
--------------------------------------------------------------
Cavitation energy (kcal/mol) = 16.10
Dispersion energy (kcal/mol) = -12.61
Repulsion energy (kcal/mol) = 0.81
Total non electrostatic (kcal/mol) = 4.30
--------------------------------------------------------------

APPLICATIONS
22
PIPEREDIN CATION (C
5
NH
12
+
),
FREE ENERGY OF HYDRATION
Method AG
solv
, kcal/mol
SP SCRF(Dipole,A0=5.5) -30.6
SP SCRF(PCM) -56.0
SP SCRF(CPCM) -56.1
SP SCRF(IPCM) -59.4
SP SCRF(SCIPCM) -60.9
Opt SCRF(PCM) -56.3
Opt SCRF(CPCM) -56.4
Opt SCRF(SCIPCM) -61.1
Experiment -60.0
23
PCM cavity was
constructed of
1006 tesserae
Dipole, IPCM and SCIPCM results includes electrostatic effects only, sum of
non-electrostatic is + 4.3 kcal/mol (PCM).
QM: HF/6-31G(d)
ET SYSTEM
24
Donor = 4-Biphenyl
Acceptor = 2-Naphthyl
Spacer: 5-a-androstane
e


D

SA DSA

ET SYSTEM
25
ET system
Method to solve
surface charges
Memory,M
b
CPUs Time,
min.
Matrix inversion
(default)
240 1 92.5
640 1 32
800 1 31
1600 1 30
1600 4 22
Iterative
64 1 28
640 1 29
800 1 27
1600 1 29
400 4 17.5
ROHF/6-31G(d,p) SP SCRF(IEFPCM, Solvent=THF)
D

SA DSA

D: 4-Biphenyl
A: 2-Naphthyl
S:5-o-androstane
87 atoms in total,
5158 tesserae created
ET SYSTEM
26
Method to solve
surface charges
Memory,M
b
CPUs Time,
min.
Matrix inversion
(default)
240 1 29
640 1 29
800 1 28
1600 1 28
1600 4 19
Iterative
64 1 16
640 1 16
800 1 16
1600 1 16
800 4 5.75
ROHF/6-31G(d,p) SP SCRF(PCM, Solvent=THF)
D

SA DSA

D: 4-Biphenyl
A: 2-Naphthyl
S:5-o-androstane
87 atoms in total,
5158 tesserae created
ET SYSTEM
27
In vacuo ROHF and UHF calculations fails to produce
the precursor state. Altering of MOs does not help.
Polarization field of solvent makes it possible to
obtain solution (with solvent polarization effects
included!) for both precursor and successor states
AG = -7.7 kcal/mol (IEFPCM)
AG = -9.6 kcal/mol (PCM)
AG = -2.7 kcal/mol (PCM, optimization, 78 hrs.)
AG = -51 kcal/mol (Experiment)

Blue structure is the precursor, 4-biphenyl is planar
Red structure is successor, 4-biphenyl dihedral angle is 42.9
using guess=alter option
and altering order of HOMO
and LUMO
MENSHUTKIN REACTION
What is AG and AG

for the reaction?

What is the nature of the transition state?
How does solvent change the result?
28
NH
3
CH
3
Cl NH
3
CH
3
+

Cl

MENSHUTKIN REACTION
Model
AG

AG
Gas 43.7 120.0
Onsager 18.2 10.0
DPCM@Onsager 24.2 -21.0
CPCM 24.8 -21.5
Experiment for CH
3
I
Gas ? 110
Solution 24 -30
Energies in kcal/mol
29
NH
3
CH
3
Cl NH
3
CH
3
+
Cl

MENSHUTKIN REACTION: TRANSITION STATE
Model C-N C-Cl H-N-C Cl-C-H
Gas 1.765 2.571 110.6 78.7
Onsager 2.273 2.250 112.6 94.2
CPCM 2.145 2.249 110.3 92.6
30
RECOMMENDATIONS
Preliminary in vacuo calculations (geometry and wavefunction
guess)
In many cases SP SCRF after Optimization in vacuo is enough
IEFPCM ( It is the default method in G03)
When memory is limited, or the system is large, the Iterative
algorithm is faster and less demanding than Inversion
When time is crucial, CPCM is recommended under some
conditions:
polar solvent;
keyword Iterative!
31