4.3 Basic SCF Job Control

4.3.1 Basic Options

In brief, Q-Chem supports the three main variants of the HF method. They are:

Restricted Hartree-Fock (RHF) for closed-shell molecules. It is typically appropriate for closed shell molecules at their equilibrium geometry, where electrons occupy orbitals in pairs.
Unrestricted Hartree-Fock (UHF) for open-shell molecules. Appropriate for radicals with an odd number of electrons, and also for molecules with even numbers of electrons where not all electrons are paired, e.g., stretched bonds and diradicals.
Restricted open-shell Hartree-Fock (ROHF) for open-shell molecules, where the $\alpha$ and $\beta$ orbitals are constrained to be identical.

Only two $rem variables are required in order to run HF calculations:

BASIS	to specify the basis set (see Chapter 7).
METHOD	SCF method: HF or a density functional (see Section 4.4).

In slightly more detail, here is a list of basic $rem variables associated with running SCF calculations. See Chapter 7 for further detail on basis sets available and Chapter 8 for specifying effective core potentials.

JOBTYPE

Specifies the type of calculation.

TYPE:

STRING

DEFAULT:

SP

OPTIONS:

SP

Single point energy.

OPT

Geometry minimization.

TS

Transition structure search.

FREQ

Frequency calculation.

FORCE

Analytical force calculation.

RPATH

Intrinsic reaction coordinate calculation.

NMR

NMR chemical shift calculation.

ISSC

Indirect nuclear spin-spin coupling calculation.

BSSE

Basis-set superposition error (counterpoise) correction.

EDA

Energy decomposition analysis.

RECOMMENDATION:

None

METHOD

Specifies the exchange-correlation functional.

TYPE:

STRING

DEFAULT:

No default

OPTIONS:

NAME

Use METHOD = NAME, where NAME is either HF for Hartree-Fock theory or

else one of the DFT methods listed in Section 4.4.3.4.

RECOMMENDATION:

In general, consult the literature to guide your selection. Our recommendations for DFT are indicated in bold in Section 4.4.3.4.

BASIS

Specifies the basis sets to be used.

TYPE:

STRING

DEFAULT:

No default basis set

OPTIONS:

General, Gen

User defined ($basis keyword required).

Symbol

Use standard basis sets as per Chapter 7.

Mixed

Use a mixture of basis sets (see Chapter 7).

RECOMMENDATION:

Consult literature and reviews to aid your selection.

PRINT_ORBITALS

Prints orbital coefficients with atom labels in analysis part of output.

TYPE:

INTEGER/LOGICAL

DEFAULT:

FALSE

OPTIONS:

FALSE

Do not print any orbitals.

TRUE

Prints occupied orbitals plus 5 virtual orbitals.

NVIRT

Number of virtual orbitals to print.

RECOMMENDATION:

Use true unless more virtual orbitals are desired.

THRESH

Cutoff for neglect of two electron integrals. $10^{-\mathrm{THRESH}}$ (THRESH $\le 14$ ).

TYPE:

INTEGER

DEFAULT:

8

For single point energies.

10

For optimizations and frequency calculations.

14

For coupled-cluster calculations.

OPTIONS:

$n$

for a threshold of $10^{-n}$ .

RECOMMENDATION:

Should be at least three greater than SCF_CONVERGENCE. Increase for more significant figures, at greater computational cost.

SCF_CONVERGENCE

SCF is considered converged when the wave function error is less that $10^{-\mathrm{SCF\_ CONVERGENCE}}$ . Adjust the value of THRESH at the same time. (Starting with Q-Chem 3.0, the DIIS error is measured by the maximum error rather than the RMS error as in earlier versions.)

TYPE:

INTEGER

DEFAULT:

5

For single point energy calculations.

8

For geometry optimizations and vibrational analysis.

8

For SSG calculations, see Chapter 5.

OPTIONS:

User-defined

RECOMMENDATION:

Tighter criteria for geometry optimization and vibration analysis. Larger values provide more significant figures, at greater computational cost.

UNRESTRICTED

Controls the use of restricted or unrestricted orbitals.

TYPE:

LOGICAL

DEFAULT:

FALSE

Closed-shell systems.

TRUE

Open-shell systems.

OPTIONS:

FALSE

Constrain the spatial part of the alpha and beta orbitals to be the same.

TRUE

Do not Constrain the spatial part of the alpha and beta orbitals.

RECOMMENDATION:

Use the default unless ROHF is desired. Note that for unrestricted calculations on systems with an even number of electrons it is usually necessary to break $\alpha$ / $\beta$ symmetry in the initial guess, by using SCF_GUESS_MIX or providing $occupied information (see Section 4.5 on initial guesses).

4.3.2 Additional Options

Listed below are a number of useful options to customize an SCF calculation. This is only a short summary of the function of these $rem variables. A full list of all SCF-related variables is provided in Appendix C. Several important sub-topics are discussed separately, including ${\cal {O}}({N})$ methods for large molecules (Section 4.8), customizing the initial guess (Section 4.5), and converging the SCF calculation (Section 4.6).

INTEGRALS_BUFFER

Controls the size of in-core integral storage buffer.

TYPE:

INTEGER

DEFAULT:

15

15 Megabytes.

OPTIONS:

User defined size.

RECOMMENDATION:

Use the default, or consult your systems administrator for hardware limits.

DIRECT_SCF

Controls direct SCF.

TYPE:

LOGICAL

DEFAULT:

Determined by program.

OPTIONS:

TRUE

Forces direct SCF.

FALSE

Do not use direct SCF.

RECOMMENDATION:

Use the default; direct SCF switches off in-core integrals.

METECO

Sets the threshold criteria for discarding shell-pairs.

TYPE:

INTEGER

DEFAULT:

2

Discard shell-pairs below $10^{-\mathrm{THRESH}}$ .

OPTIONS:

1

Discard shell-pairs four orders of magnitude below machine precision.

2

Discard shell-pairs below 10 $^{-\mathrm{THRESH}}$ .

RECOMMENDATION:

Use the default.

STABILITY_ANALYSIS

Performs stability analysis for a HF or DFT solution.

TYPE:

LOGICAL

DEFAULT:

FALSE

OPTIONS:

TRUE

Perform stability analysis.

FALSE

Do not perform stability analysis.

RECOMMENDATION:

Set to TRUE when a HF or DFT solution is suspected to be unstable.

SCF_PRINT

Controls level of output from SCF procedure to Q-Chem output file.

TYPE:

INTEGER

DEFAULT:

0

Minimal, concise, useful and necessary output.

OPTIONS:

0

Minimal, concise, useful and necessary output.

1

Level 0 plus component breakdown of SCF electronic energy.

2

Level 1 plus density, Fock and MO matrices on each cycle.

3

Level 2 plus two-electron Fock matrix components (Coulomb, HF exchange

and DFT exchange-correlation matrices) on each cycle.

RECOMMENDATION:

Proceed with care; can result in extremely large output files at level 2 or higher. These levels are primarily for program debugging.

SCF_FINAL_PRINT

Controls level of output from SCF procedure to Q-Chem output file at the end of the SCF.

TYPE:

INTEGER

DEFAULT:

0

No extra print out.

OPTIONS:

0

No extra print out.

1

Orbital energies and break-down of SCF energy.

2

Level 1 plus MOs and density matrices.

3

Level 2 plus Fock and density matrices.

RECOMMENDATION:

The break-down of energies is often useful (level 1).

KS_GAP_PRINT

Control printing of (generalized Kohn-Sham) HOMO-LUMO gap information.

TYPE:

Boolean

DEFAULT:

false

OPTIONS:

false

(default) do not print gap information

true

print gap information

RECOMMENDATION:

Use in conjunction with KS_GAP_UNIT if true.

KS_GAP_UNIT

Unit for KS_GAP_PRINT and FOA_FUNDGAP (see Section 4.4.10)

TYPE:

INTEGER

DEFAULT:

0

OPTIONS:

0

(default) hartrees

1

eV

RECOMMENDATION:

none

DIIS_SEPARATE_ERRVEC

Control optimization of DIIS error vector in unrestricted calculations.

TYPE:

LOGICAL

DEFAULT:

FALSE

Use a combined $\alpha$ and $\beta$ error vector.

OPTIONS:

FALSE

Use a combined $\alpha$ and $\beta$ error vector.

TRUE

Use separate error vectors for the $\alpha$ and $\beta$ spaces.

RECOMMENDATION:

When using DIIS in Q-Chem a convenient optimization for unrestricted calculations is to sum the $\alpha$ and $\beta$ error vectors into a single vector which is used for extrapolation. This is often extremely effective, but in some pathological systems with symmetry breaking, can lead to false solutions being detected, where the $\alpha$ and $\beta$ components of the error vector cancel exactly giving a zero DIIS error. While an extremely uncommon occurrence, if it is suspected, set DIIS_SEPARATE_ERRVEC = TRUE to check.

4.3.3 Examples

Provided below are examples of Q-Chem input files to run ground state, HF single point energy calculations.

Example 4.17 Example Q-Chem input for a single point energy calculation on water. Note that the declaration of the single point $rem variable and level of theory to treat correlation are redundant because they are the same as the Q-Chem defaults.

$molecule
   0  1
   O
   H1  O  oh
   H2  O  oh  H1  hoh

   oh  =   1.2
   hoh = 120.0
$end

$rem
   JOBTYPE       sp       Single Point energy
   METHOD        hf       Hartree-Fock
   BASIS         sto-3g   Basis set
$end

$comment
HF/STO-3G water single point calculation
$end

Example 4.18 UHF/6-311G calculation on the Li atom. Note that correlation and the job type were not indicated because Q-Chem defaults automatically to no correlation and single point energies. Note also that, since the number of $\alpha$ and $\beta$ electron differ, MOs default to an unrestricted formalism.

$molecule
   0,2
   3
$end

$rem
   METHOD     HF       Hartree-Fock
   BASIS      6-311G   Basis set
$end

Example 4.19 ROHF/6-311G calculation on the Lithium atom. Note again that correlation and the job type need not be indicated.

$molecule
   0,2
   3
$end

$rem
   METHOD         hf       Hartree-Fock
   UNRESTRICTED   false    Restricted MOs
   BASIS          6-311G   Basis set
$end

Example 4.20 RHF/6-31G stability analysis calculation on the singlet state of the oxygen molecule. The wave function is RHF $\rightarrow$ UHF unstable.

$molecule
   0 1
   O
   O  1  1.165
$end

$rem
   METHOD               hf         Hartree-Fock
   UNRESTRICTED         false      Restricted MOs
   BASIS                6-31G(d)   Basis set
   STABILITY_ANALYSIS   true       Perform a stability analysis
$end

4.3.4 Symmetry

Symmetry is a powerful branch of mathematics and is often exploited in quantum chemistry, both to reduce the computational workload and to classify the final results obtained [17, 18, 19]. Q-Chem is able to determine the point group symmetry of the molecular nuclei and, on completion of the SCF procedure, classify the symmetry of molecular orbitals, and provide symmetry decomposition of kinetic and nuclear attraction energy (see Chapter 10).

Molecular systems possessing point group symmetry offer the possibility of large savings of computational time, by avoiding calculations of integrals which are equivalent i.e., those integrals which can be mapped on to one another under one of the symmetry operations of the molecular point group. The Q-Chem default is to use symmetry to reduce computational time, when possible.

There are several keywords that are related to symmetry, which causes frequent confusion. SYM_IGNORE controls symmetry throughout all modules. The default is FALSE. In some cases it may be desirable to turn off symmetry altogether, for example if you do not want Q-Chem to reorient the molecule into the standard nuclear orientation, or if you want to turn it off for finite difference calculations. If the SYM_IGNORE keyword is set to TRUE then the coordinates will not be altered from the input, and the point group will be set to $C_1$ .

The SYMMETRY keyword controls symmetry in some integral routines. It is set to FALSE by default. Note that setting it to FALSE does not turn point group symmetry off, and does not disable symmetry in the coupled-cluster suite (CCMAN and CCMAN2), which is controlled by CC_SYMMETRY (see Chapters 5 and 6), although we noticed that sometimes it may interfere with the determination of orbital symmetries, possibly due to numerical noise. In some cases, SYMMETRY = TRUE can cause problems (poor convergence and wildly incorrect SCF energies) and turning it off can avoid these problems.

Note: The user should be aware about different conventions for defining symmetry elements. The arbitrariness affects, for example, $C_{2v}$ point group. The specific choice affects how the irreps in the affected groups are labeled. For example, $b_1$ and $b_2$ irreps in $C_{2v}$ are flipped when using different conventions. Q-Chem uses non-Mulliken symmetry convention. See http://iopenshell.usc.edu/howto/symmetry for detailed explanations.

SYMMETRY

Controls the efficiency through the use of point group symmetry for calculating integrals.

TYPE:

LOGICAL

DEFAULT:

TRUE

Use symmetry for computing integrals.

OPTIONS:

TRUE

Use symmetry when available.

FALSE

Do not use symmetry. This is always the case for RIMP2 jobs

RECOMMENDATION:

Use the default unless benchmarking. Note that symmetry usage is disabled for RIMP2, FFT, and QM/MM jobs.

SYM_IGNORE

Controls whether or not Q-Chem determines the point group of the molecule and reorients the molecule to the standard orientation.

TYPE:

LOGICAL

DEFAULT:

FALSE

Do determine the point group (disabled for RIMP2 jobs).

OPTIONS:

TRUE/FALSE

RECOMMENDATION:

Use the default unless you do not want the molecule to be reoriented. Note that symmetry usage is disabled for RIMP2 jobs.

SYM_TOL

Controls the tolerance for determining point group symmetry. Differences in atom locations less than $10^{-\mathrm{SYM\_ TOL}}$ are treated as zero.

TYPE:

INTEGER

DEFAULT:

5

Corresponding to $10^{-5}$ .

OPTIONS:

User defined.

RECOMMENDATION:

Use the default unless the molecule has high symmetry which is not being correctly identified. Note that relaxing this tolerance too much may introduce errors into the calculation.

SP	Single point energy.
OPT	Geometry minimization.
TS	Transition structure search.
FREQ	Frequency calculation.
FORCE	Analytical force calculation.
RPATH	Intrinsic reaction coordinate calculation.
NMR	NMR chemical shift calculation.
ISSC	Indirect nuclear spin-spin coupling calculation.
BSSE	Basis-set superposition error (counterpoise) correction.
EDA	Energy decomposition analysis.

NAME	Use METHOD = NAME, where NAME is either HF for Hartree-Fock theory or
	else one of the DFT methods listed in Section 4.4.3.4.

General, Gen	User defined ($basis keyword required).
Symbol	Use standard basis sets as per Chapter 7.
Mixed	Use a mixture of basis sets (see Chapter 7).

FALSE	Do not print any orbitals.
TRUE	Prints occupied orbitals plus 5 virtual orbitals.
NVIRT	Number of virtual orbitals to print.

8	For single point energies.
10	For optimizations and frequency calculations.
14	For coupled-cluster calculations.

5	For single point energy calculations.
8	For geometry optimizations and vibrational analysis.
8	For SSG calculations, see Chapter 5.

FALSE	Constrain the spatial part of the alpha and beta orbitals to be the same.
TRUE	Do not Constrain the spatial part of the alpha and beta orbitals.

1	Discard shell-pairs four orders of magnitude below machine precision.
2	Discard shell-pairs below 10 $^{-\mathrm{THRESH}}$ .

TRUE	Perform stability analysis.
FALSE	Do not perform stability analysis.

0	Minimal, concise, useful and necessary output.
1	Level 0 plus component breakdown of SCF electronic energy.
2	Level 1 plus density, Fock and MO matrices on each cycle.
3	Level 2 plus two-electron Fock matrix components (Coulomb, HF exchange
	and DFT exchange-correlation matrices) on each cycle.

0	No extra print out.
1	Orbital energies and break-down of SCF energy.
2	Level 1 plus MOs and density matrices.
3	Level 2 plus Fock and density matrices.

false	(default) do not print gap information
true	print gap information

FALSE	Use a combined $\alpha$ and $\beta$ error vector.
TRUE	Use separate error vectors for the $\alpha$ and $\beta$ spaces.

TRUE	Use symmetry when available.
FALSE	Do not use symmetry. This is always the case for RIMP2 jobs