- Description
- Options
- Availability
- Related Keywords
- Examples
Description
This calculation type keyword requests that a reaction path be followed by integrating the intrinsic reaction coordinate [Fukui81, Hratchian05a]. The initial geometry (given in the molecule specification section) is that of the transition state, and the path can be followed in one or both directions from that point. The forward direction is defined as the direction the transition vector is pointing when the largest component of the transition vector (“phase”) is positive; it can be defined explicitly using the Phase option. By default, both reaction path directions are followed.
IRC calculations require initial force constants to proceed. You must provide these to the calculation in some way. The usual method is to save the checkpoint file from the preceding frequency calculation (used to verify that the optimized geometry to be used in the IRC calculation is in fact a transition state), and then specify the RCFC option in the route section. Another possibility is to compute them at the beginning of the IRC calculation (CalcFC). Note that one of RCFC and CalcFC must be specified (CalcAll is also available but is not typically necessary with the HPC algorithm).
In Gaussian 16, most calculations use the HPC algorithm [Hratchian04a, Hratchian05a, Hratchian05b] by default (introduced in Gaussian 09). It is much more efficient than the one used in earlier program versions. ONIOM(MO:MM) calculations use the Euler predictor-corrector integration algorithm. This same integrator is also used by default in calculations using methods with gradients but without analytic second derivatives; such calculations should include the GradientOnly option. Available algorithms are discussed in Availability.
The default is to report only the energies and reaction coordinate at each point on the path; if geometrical parameters along the path are desired, these should be defined as redundant internal coordinates via Geom=ModRedundant or as input to the IRC code via IRC(Report=Read) (see Options for the latter’s input format).
You can specify alternative isotopes for IRC jobs using the ReadIsotopes option (described in Options).
Options
Path Specification Options
Phase=(N1, N2 [,N3 [,N4]])
Defines the phase for the transition vector such that forward motion along the transition vector corresponds to an increase in the specified internal coordinate, designated by up to four atom numbers. If two atom numbers are given, the coordinate is a bond stretch between the two atoms; three atom numbers specify an angle bend; and four atoms define a dihedral angle.
Forward
Follow the path only in the forward direction.
Reverse
Follow the path only in the reverse direction.
Downhill
Proceed downhill from the input geometry.
MaxPoints=N
Number of points along the reaction path to examine (in each direction if both are being considered). The default is 10.
StepSize=N
Step size along the reaction path, in units of 0.01 Bohr. If N<0, then the step size is taken in units of 0.01 amu1/2-Bohr. The default is 10.
ReadIsotopes
This option allows you to specify alternatives to the default temperature, pressure, frequency scale factor and/or isotopes—298.15 K, 1 atmosphere, no scaling, and the most abundant isotopes (respectively). It is useful when you want to rerun an analysis using different parameters from the data in a checkpoint file.
Be aware, however, that all of these can be specified in the route section (Temperature, Pressure and Scale keywords) and molecule specification (the Iso parameter), as in this example:
#T Method/6-31G(d) JobType Temperature=300.0 … … 0 1 C(Iso=13) …
ReadIsotopes input has the following format:
| temp pressure [scale] | Values must be real numbers. |
| isotope mass for atom 1 | |
| isotope mass for atom 2 | |
| … | |
| isotope mass for atom n |
Where temp, pressure, and scale are the desired temperature, pressure, and an optional scale factor for frequency data when used for thermochemical analysis (the default is unscaled). The remaining lines hold the isotope masses for the various atoms in the molecule, arranged in the same order as they appeared in the molecule specification section. If integers are used to specify the atomic masses, the program will automatically use the corresponding actual exact isotopic mass (e.g., 18 specifies 18O, and Gaussian uses the value 17.99916).
Algorithm Selection Options
HPC
Use the Hessian-based Predictor-Corrector integrator [Hratchian04a, Hratchian05a, Hratchian05b]: a very accurate algorithm that uses the Hessian-based local quadratic approximation as the predictor component and a modified Bulrisch-Stoer integrator for the corrector portion. This corrector integrator is done using a distance-weighted interpolant surface [Collins02] fitted to energies, gradients, and Hessians at the beginning and ending points of the predictor step. This is the default for most calculations. Note that it is not practical for extremely large molecular systems.
EulerPC
Use the first-order Euler integration for the predictor step along with the HPC corrector step. This is the default for IRC=GradientOnly calculations. This is also the default algorithm for IRC calculations using an ONIOM(MO:MM) method. It is a practical choice for such calculations on large molecules.
LQA
Use the local quadratic approximation [Page88, Page90] for the predictor step.
DVV
Use the damped velocity verlet integrator [Hratchian02].
Euler
Use only the first-order Euler integration predictor step for the IRC. This option is not recommended for production use.
ReCalc=N
Compute the Hessian analytically every N predictor steps or every |N| corrector steps if N<0. Analytic second derivatives can be requested intermittently during IRCs using IRC=(CalcFC,RecalcFC=(Predictor=N,Corrector=M)), which computes second derivatives at the initial point and then at every Nth predictor step and every Mth corrector step. You must still specify RCFC or CalcFC to provide the initial Hessian. Update is a synonym for ReCalc. Requires a method which has analytic second derivatives.
GradientOnly
Use an algorithm that does not require second derivatives. Note that you must specify this option explicitly for such methods (they are not automatically detected). Can be combined with EulerPC (the default), HPC, Euler, or DVV.
Coordinate System Selection Options
MassWeighted
Follow the path in mass-weighted Cartesian coordinates. MW is a synonym for MassWeighted. This is the default.
Cartesian
Follow the path in Cartesian coordinates without mass-weighting.
Options For Generating Initial Force Constants
RCFC
Specifies that the computed force constants in Cartesian coordinates from a frequency calculation are to be read from the checkpoint file. ReadCartesianFC is a synonym for RCFC.
CalcFC
Specifies that the force constants be computed at the first point.
Procedure-Related Options
Restart
Restarts an IRC calculation that did not complete, or restarts an IRC calculation which did complete, but for which additional points along the path are desired.
Report[=item]
Controls which geometric parameters are reported by an IRC. By default, no geometrical parameters are reported. Report without a parameter includes all of the generated internal coordinates. The possible values for item are:
| Read | Read a list of internal coordinates to report. These are specified as 1-4 atom numbers only (ModRedundant-style coordinate specifications are not supported). |
| Bonds | Reports bonds from the internal coordinates (if present). |
| Angles | Reports angles from the internal coordinates (if present). |
| Dihedrals | Reports dihedrals from the internal coordinates (if present). |
| Cartesians | Reports all Cartesian coordinates. |
ReCorrect[=when]
Controls testing-and-recomputing for the correction step of HPC and EulerPC IRCs. ReCorrect (without a parameter) and ReCorrect=Yes say to repeat the corrector step whenever the correction is greater than the threshold (which can be decreased with the Tight and VTight options). The parameter can take on the following values:
| Never | Do not repeat correction steps (i.e., suppress the threshold test). |
| Always | Always recompute the corrector at least once regardless of the size of the initial correction. |
| Test | Test the quality of the corrector step and report the results, but do not take an additional corrector step. The computed IRC path will be the same as with ReCorrect=Never. |
The default is Yes for EulerPC and HPC, and Never for other integrators.
MaxCycle=N
Sets the maximum number of steps to N. The default is 20.
Tight
This option tightens the cutoffs on forces and step size that are used to determine convergence. For DFT calculations, Int=UltraFine should be specified as well.
VeryTight
Extremely tight optimization convergence criteria. VTight is a synonym for VeryTight. For DFT calculations, Int=UltraFine should be specified as well.
Options For Compatibility with Gaussian 03
The GS2 option requests the IRC algorithm used in Gaussian 03 within the new IRC implementation. Use the keyword Use=L115 in order to run the code that was the default in Gaussian 03 (recommended for reproducing old results only).
GS2
Use the IRC algorithm that was the default in Gaussian 03 and earlier [Gonzalez89, Gonzalez90]. The geometry is optimized at each point along the reaction path such that the segment of the reaction path between any two adjacent points is described by an arc of a circle and so that the gradients at the end points of the arc are tangent to the path. By default, a GS2 IRC calculation steps 6 points in mass-weighted internal coordinates in the forward direction and 6 points in the reverse direction, in steps of 0.1 amu1/2 Bohr along the path.
CalcAll
Specifies that the force constants be computed at every point.
Availability
The default algorithms are available for HF, all DFT methods, CIS, TD, MP2, MP3, MP4(SDQ), CID, CISD, CCD, CCSD, QCISD, BD, CASSCF, and all semi-empirical methods.
Examples
When the IRC has completed, the program prints a table summarizing the results:
Reaction path calculation complete.
Energies reported relative to the TS energy of -91.564851
----------------------------------------------------------------------
Summary of reaction path following
----------------------------------------------------------------------
Energy Rx Coord
1 -0.00880 -0.54062
2 -0.00567 -0.43250
3 -0.00320 -0.32438
4 -0.00142 -0.21626
5 -0.00035 -0.10815
6 0.00000 0.00000 transition state
7 -0.00034 0.10815
8 -0.00131 0.21627
9 -0.00285 0.32439
10 -0.00487 0.43252
11 -0.00725 0.54065
----------------------------------------------------------------------
The initial geometry (transition structure) appears in the middle of the table (in this case, as point 6). It can be identified quickly by looking for reaction coordinate and energy values of 0.00000.
- Description
- Options
- Availability
- Related Keywords
- Examples
This calculation type keyword requests that a reaction path be followed by integrating the intrinsic reaction coordinate [Fukui81, Hratchian05a]. The initial geometry (given in the molecule specification section) is that of the transition state, and the path can be followed in one or both directions from that point. The forward direction is defined as the direction the transition vector is pointing when the largest component of the transition vector (“phase”) is positive; it can be defined explicitly using the Phase option. By default, both reaction path directions are followed.
IRC calculations require initial force constants to proceed. You must provide these to the calculation in some way. The usual method is to save the checkpoint file from the preceding frequency calculation (used to verify that the optimized geometry to be used in the IRC calculation is in fact a transition state), and then specify the RCFC option in the route section. Another possibility is to compute them at the beginning of the IRC calculation (CalcFC). Note that one of RCFC and CalcFC must be specified (CalcAll is also available but is not typically necessary with the HPC algorithm).
In Gaussian 16, most calculations use the HPC algorithm [Hratchian04a, Hratchian05a, Hratchian05b] by default (introduced in Gaussian 09). It is much more efficient than the one used in earlier program versions. ONIOM(MO:MM) calculations use the Euler predictor-corrector integration algorithm. This same integrator is also used by default in calculations using methods with gradients but without analytic second derivatives; such calculations should include the GradientOnly option. Available algorithms are discussed in Availability.
The default is to report only the energies and reaction coordinate at each point on the path; if geometrical parameters along the path are desired, these should be defined as redundant internal coordinates via Geom=ModRedundant or as input to the IRC code via IRC(Report=Read) (see Options for the latter’s input format).
You can specify alternative isotopes for IRC jobs using the ReadIsotopes option (described in Options).
Path Specification Options
Phase=(N1, N2 [,N3 [,N4]])
Defines the phase for the transition vector such that forward motion along the transition vector corresponds to an increase in the specified internal coordinate, designated by up to four atom numbers. If two atom numbers are given, the coordinate is a bond stretch between the two atoms; three atom numbers specify an angle bend; and four atoms define a dihedral angle.
Forward
Follow the path only in the forward direction.
Reverse
Follow the path only in the reverse direction.
Downhill
Proceed downhill from the input geometry.
MaxPoints=N
Number of points along the reaction path to examine (in each direction if both are being considered). The default is 10.
StepSize=N
Step size along the reaction path, in units of 0.01 Bohr. If N1/2-Bohr. The default is 10.
ReadIsotopes
This option allows you to specify alternatives to the default temperature, pressure, frequency scale factor and/or isotopes—298.15 K, 1 atmosphere, no scaling, and the most abundant isotopes (respectively). It is useful when you want to rerun an analysis using different parameters from the data in a checkpoint file.
Be aware, however, that all of these can be specified in the route section (Temperature, Pressure and Scale keywords) and molecule specification (the Iso parameter), as in this example:
#T Method/6-31G(d) JobType Temperature=300.0 … … 0 1 C(Iso=13) …
ReadIsotopes input has the following format:
| temp pressure [scale] | Values must be real numbers. |
| isotope mass for atom 1 | |
| isotope mass for atom 2 | |
| … | |
| isotope mass for atom n |
Where temp, pressure, and scale are the desired temperature, pressure, and an optional scale factor for frequency data when used for thermochemical analysis (the default is unscaled). The remaining lines hold the isotope masses for the various atoms in the molecule, arranged in the same order as they appeared in the molecule specification section. If integers are used to specify the atomic masses, the program will automatically use the corresponding actual exact isotopic mass (e.g., 18 specifies 18O, and Gaussian uses the value 17.99916).
Algorithm Selection Options
HPC
Use the Hessian-based Predictor-Corrector integrator [Hratchian04a, Hratchian05a, Hratchian05b]: a very accurate algorithm that uses the Hessian-based local quadratic approximation as the predictor component and a modified Bulrisch-Stoer integrator for the corrector portion. This corrector integrator is done using a distance-weighted interpolant surface [Collins02] fitted to energies, gradients, and Hessians at the beginning and ending points of the predictor step. This is the default for most calculations. Note that it is not practical for extremely large molecular systems.
EulerPC
Use the first-order Euler integration for the predictor step along with the HPC corrector step. This is the default for IRC=GradientOnly calculations. This is also the default algorithm for IRC calculations using an ONIOM(MO:MM) method. It is a practical choice for such calculations on large molecules.
LQA
Use the local quadratic approximation [Page88, Page90] for the predictor step.
DVV
Use the damped velocity verlet integrator [Hratchian02].
Euler
Use only the first-order Euler integration predictor step for the IRC. This option is not recommended for production use.
ReCalc=N
Compute the Hessian analytically every N predictor steps or every |N| corrector steps if NIRC=(CalcFC,RecalcFC=(Predictor=N,Corrector=M)), which computes second derivatives at the initial point and then at every Nth predictor step and every Mth corrector step. You must still specify RCFC or CalcFC to provide the initial Hessian. Update is a synonym for ReCalc. Requires a method which has analytic second derivatives.
GradientOnly
Use an algorithm that does not require second derivatives. Note that you must specify this option explicitly for such methods (they are not automatically detected). Can be combined with EulerPC (the default), HPC, Euler, or DVV.
Coordinate System Selection Options
MassWeighted
Follow the path in mass-weighted Cartesian coordinates. MW is a synonym for MassWeighted. This is the default.
Cartesian
Follow the path in Cartesian coordinates without mass-weighting.
Options For Generating Initial Force Constants
RCFC
Specifies that the computed force constants in Cartesian coordinates from a frequency calculation are to be read from the checkpoint file. ReadCartesianFC is a synonym for RCFC.
CalcFC
Specifies that the force constants be computed at the first point.
Procedure-Related Options
Restart
Restarts an IRC calculation that did not complete, or restarts an IRC calculation which did complete, but for which additional points along the path are desired.
Report[=item]
Controls which geometric parameters are reported by an IRC. By default, no geometrical parameters are reported. Report without a parameter includes all of the generated internal coordinates. The possible values for item are:
| Read | Read a list of internal coordinates to report. These are specified as 1-4 atom numbers only (ModRedundant-style coordinate specifications are not supported). |
| Bonds | Reports bonds from the internal coordinates (if present). |
| Angles | Reports angles from the internal coordinates (if present). |
| Dihedrals | Reports dihedrals from the internal coordinates (if present). |
| Cartesians | Reports all Cartesian coordinates. |
ReCorrect[=when]
Controls testing-and-recomputing for the correction step of HPC and EulerPC IRCs. ReCorrect (without a parameter) and ReCorrect=Yes say to repeat the corrector step whenever the correction is greater than the threshold (which can be decreased with the Tight and VTight options). The parameter can take on the following values:
| Never | Do not repeat correction steps (i.e., suppress the threshold test). |
| Always | Always recompute the corrector at least once regardless of the size of the initial correction. |
| Test | Test the quality of the corrector step and report the results, but do not take an additional corrector step. The computed IRC path will be the same as with ReCorrect=Never. |
The default is Yes for EulerPC and HPC, and Never for other integrators.
MaxCycle=N
Sets the maximum number of steps to N. The default is 20.
Tight
This option tightens the cutoffs on forces and step size that are used to determine convergence. For DFT calculations, Int=UltraFine should be specified as well.
VeryTight
Extremely tight optimization convergence criteria. VTight is a synonym for VeryTight. For DFT calculations, Int=UltraFine should be specified as well.
Options For Compatibility with Gaussian 03
The GS2 option requests the IRC algorithm used in Gaussian 03 within the new IRC implementation. Use the keyword Use=L115 in order to run the code that was the default in Gaussian 03 (recommended for reproducing old results only).
GS2
Use the IRC algorithm that was the default in Gaussian 03 and earlier [Gonzalez89, Gonzalez90]. The geometry is optimized at each point along the reaction path such that the segment of the reaction path between any two adjacent points is described by an arc of a circle and so that the gradients at the end points of the arc are tangent to the path. By default, a GS2 IRC calculation steps 6 points in mass-weighted internal coordinates in the forward direction and 6 points in the reverse direction, in steps of 0.1 amu1/2 Bohr along the path.
CalcAll
Specifies that the force constants be computed at every point.
The default algorithms are available for HF, all DFT methods, CIS, TD, MP2, MP3, MP4(SDQ), CID, CISD, CCD, CCSD, QCISD, BD, CASSCF, and all semi-empirical methods.
When the IRC has completed, the program prints a table summarizing the results:
Reaction path calculation complete.
Energies reported relative to the TS energy of -91.564851
----------------------------------------------------------------------
Summary of reaction path following
----------------------------------------------------------------------
Energy Rx Coord
1 -0.00880 -0.54062
2 -0.00567 -0.43250
3 -0.00320 -0.32438
4 -0.00142 -0.21626
5 -0.00035 -0.10815
6 0.00000 0.00000 transition state
7 -0.00034 0.10815
8 -0.00131 0.21627
9 -0.00285 0.32439
10 -0.00487 0.43252
11 -0.00725 0.54065
----------------------------------------------------------------------
The initial geometry (transition structure) appears in the middle of the table (in this case, as point 6). It can be identified quickly by looking for reaction coordinate and energy values of 0.00000.
Last updated on: 19 February 2018. [G16 Rev. C.01]
