1

Minnesota Functional Module

Version 2.0

Subroutines for evaluating the M05, M05-2X, M06-L, M06-HF, M06, M06-2X,
M08-HX, M08-SO, M11, M11-L, MN12-L, GAM, MN15-L, MN15, SOGGA,
SOGGA11, SOGGA11-X, N12, N12-SX Functionals

Documentation

Haoyu S. Yu, a Yan Zhao,b Roberto Peverati,c and Donald G. Truhlard

Department of Chemistry and Supercomputing Institute,

University of Minnesota, Minneapolis, MN 55455-0431

a Present affiliation: Department of Chemistry, University of Minnesota

b Present affiliation: Hewlett-Packard Co.
c Present affiliation: Lawrence Berkeley National Laboratory, University of California, Berkeley.
d Email: truhlar@umn.edu

Date of code completion: January 27, 2016

Date of most recent change in this manual: April 6, 2016

Contents

Executive summary ..........................................................................................................................................3

Literature references – original references for functionals...............................................................................3
Literature references – review ..........................................................................................................................5
Input and output ................................................................................................................................................5
Notes .................................................................................................................................................................5
Reference energies and gradients .....................................................................................................................8
Version History 14

Executive summary
Minnesota Functional Module is a Fortran77 code for evaluating the M05, M05-2X, M06-L, M06-HF,
M06, M06-2X, M08-HX, M08-SO, M11, M11-L, MN12-L, MN12-SX, GAM, MN15-L, MN15, SOGGA,
SOGGA11, SOGGA11-X, N12 and N12-SX density functionals. The subroutines are in the accompanying
tar file.

Literature references
A. Original references for functionals
M05

Zhao, Y.; Schultz, N. E.; Truhlar, D. G. J. Chem. Phys. 2005, 123, 161103.

M05-2X

Zhao, Y.; Schultz, N. E.; Truhlar, D. G. J. Chem. Theory Comput. 2006, 2,364.

M06-L

Zhao, Y.; Truhlar, D. G. J. Chem. Phys. 2006, 125, 194101.

M06-HF

Zhao, Y.; Truhlar, D. G. J. Phys. Chem. A 2006, 110, 13126.

M06 and M06-2X

Zhao, Y.; Truhlar, D. G. Theor. Chem. Acc. 2008, 120, 215.

M08-HX and M08-SO

Zhao, Y.; Truhlar, D. G. J. Chem. Theory Comput. 2008, 4, 1849.

M11

Peverati, R.; Truhlar, D. G. J. Phys. Chem. Lett. 2011, 2, 2810.

Note that in eqs 21 and 22 of the M11 paper, Y should be X/100.

M11-L

Peverati, R.; Truhlar, D. G. J. Phys. Chem. Lett. 2012, 3, 117.

MN12-L

Peverati, R.; Truhlar, D. G. Phys. Chem. Chem. Phys. 2012, 14, 13171.

MN12-SX

Peverati, R.; Truhlar, D. G. Phys. Chem. Chem. Phys. 2012, 14, 16187.

SOGGA

Zhao, Y.; Truhlar, D. G. J. Chem. Phys. 2008, 128, 184109.

SOGGA11

Peverati, R.; Zhao, Y.; Truhlar, D. G. J. Phys. Chem. Lett. 2011, 2011, 2, 1911-1997.

Note that there is a typo in eq. 3 of the SOGGA11 paper. The correct expression is:

i
⎛ ⎞
m
⎜ 1 ⎟
g1x = ∑ aix ⎜ 1 −
µ 2⎟
i=0 ⎜⎝ 1 + s ⎟⎠
κ

SOGGA11-X
Peverati, R.; D. G. Truhlar, J. Chem. Phys. 2011, 135, 191102.

N12
Peverati, R.; Truhlar, D. G. J. Chem. Theory Comput. 2012, 8, 2310.

N12-SX
Peverati, R.; Truhlar, D. G. Phys. Chem. Chem. Phys. 2012, 14, 16187.

GAM
Yu, H. S.; Zhang, W.; Verma, P.; He, X.; Truhlar, D. G. Phys. Chem. Chem. Phys. 2015, 17, 12146.

MN15-L
Yu, H. S.; He, X.; Truhlar, D. G. J. Chem. Theory Comput. 2016, 12, 1280-1293.
dx.doi.org/10.1021/acs.jctc.5b01082

MN15
Yu, H. S.; He, X.; Li, S.; Truhlar, D. G. Chemical Science 2016, online as Accepted Manuscript.
dx.doi.org/10.1039/C6SC00705H

B. Review
Zhao, Y.; Truhlar, D. G. Acc. Chem. Res. 2008, 41, 157.

Input and output

INPUT:
RA, RB - Spin densities
D1RA, D1RB - Spin density gradients
TA, TB - τσ and τβ
NGrid - total number of grid points at which the functional is evaluated.

OUTPUT:
F - Functional values on the grids
D1F - First derivatives with respect to RA, RB, GA, GB, TA, TB on the grids

Notes
1. We used Becke’s definition (J. Chem. Phys. 104 1040 (1996)) of τσ and τβ. By this definition they
are two times larger than spin kinetic energy densities.
2. The correlation part of all Minnesota functionals needs to use the local spin density part of the
Perdew-Wang-91 correlation functional (Phys. Rev. B 45, 13244 (1992)), which is a fit to the
correlation energy of a uniform electron gas (lsdac subroutine). Since we are not allowed to
distribute the work of others, users should provide their own subroutine for this LSDA
correlation functional, or they may find help on the author’s (Kieron Burke) web site at:
http://www.chem.uci.edu/~kieron/dftold2/pubs/PBE.asc
http://www.chem.uci.edu/~kieron/dftold2/pubs/PBEsol.html
3. The correlation part of all M08-class functionals also needs to use the H(rs,ζ,t) function in the PBE
correlation (PBEH0 subroutine). As for the previous point, we are not allowed to distribute this
subroutine and users should provide their own, or they may find help on the author’s (Kieron
Burke) web site at:
http://www.chem.uci.edu/~kieron/dftold2/pubs/PBE.asc
http://www.chem.uci.edu/~kieron/dftold2/pubs/PBEsol.html
4. The correlation parts of the N12, GAM, and N12-SX are obtained from B97-like expansion
truncated at the fourth order, with the opposite spin contribution calculated as:
⎧⎪ n ⎫⎪
αβ ∑ i cαβ ⎬
Ecαβ = ∫ drε cUEG i
⎨ b u
⎩⎪i=0 ⎭⎪
and the same spin contribution calculated as:
⎧⎪ n′ i ⎫⎪
σσ ⎨ ∑ ci ucσσ ⎬
Ecσσ = ∫ drε cUEG
⎩⎪i=0 ⎭⎪
once again, users should provide their own subroutine for this, and use the parameters in Table 1.
Note that there is a typo in the N12 paper, the corrected values for bi and ci have been showed
below.
Table 1. Parameters of the B97-like expansion for the N12, GAM, and N12-SX correlation
functionals.
N12 GAM N12-SX
b0 1.00000D+00 0.860548D+00 2.63373D+00
b1 3.24511D+00 -2.94135D+00 -1.05450D+00
b2 -2.52893D+01 15.4176D+00 -7.29853D-01

b3 1.44407D+01 -5.99825D+00 4.94024D+00

b4 1.96870D+01 -23.4119D+00 -7.31760D+00
c0 1.00000D+00 0.231765D+00 8.33615D-01
c1 -5.53170D+00 0.575592D+00 3.24128D+00
c2 3.07958D+01 -3.43391D+00 -1.06407D+01
c3 -5.64196D+01 5.77281D+00 -1.60471D+01
c4 3.21250D+01 9.52449D+00 2.51047D+01

5. One needs to add a portion of the Hartree-Fock exchange energy to the total exchange-correlation
energy for the M05, M05-2X, M06, M06-2X, M06-HF, M08-HX, M08-SO, SOGGA11-X, and
MN15 functionals. See the details in Table 2.
6. The exchange part of M11 requires range-separation with the error function with 42.8% short-range
HF exchange, and 100% long-range HF exchange. The range parameter ω is 0.25.
7. The exchange part of N12-SX and MN12-SX requires 25% of “screened exchange”, which is: 25%
short-range HF exchange and 0% long-range HF exchange. The range parameter µ is 0.11.

Table 2. Hartree-Fock exchange energies in the Minnesota functionals

Functional Fraction of Hartree-Fock exchange energy
M05 0.28EHFE
M05-2X 0.56EHFE
M06 0.27EHFE
M06-2X 0.54EHFE
M06-HF 1.0EHFE
M08-HX 0.5223EHFE
M08-SO 0.5679EHFE
M11 0.428ESR-HFE + 1.0ELR-HFE (ω = 0.25)
N12-SX, MN12-SX 0.25ESX (µ = 0.11)
SOGGA, SOGGA11, M06-L, 0
M11-L, MN15
MN12-L, N12 0.44 EHFE
SOGGA11-X 0.4015EHFE

EHFE is the Hartree-Fock exchange energy, ESR-HFE and ELR-HFE are the short-range and long-
range Hartree–Fock exchange energies respectively, and ESX is the short-range Hartree–Fock
“screened” exchange.

Reference energies and gradients

Table 3 and 4 present reference energies and forces of CH3 (open shell, doublet) and H2O (closed shell,
singlet) with the 6-31+G** basis set and a pruned (99,590) grid.
Geometries of CH3 (in angstrom)
*****************************************************
C 0.000000 0.000000 0.000000
H 0.000000 1.078000 0.000000
H 0.933000 -0.539000 0.000000
H -0.933000 -0.539000 0.000000
*****************************************************

Table 3. Reference energies (Eh) and forces (X,Y,Z, Eh/a0) for CH3
PW6B95 E= -39.888691
C 0.000000 0.000294 0.000000
H 0.000000 0.000371 0.000000
H 0.000665 -0.000333 0.000000
H -0.000665 -0.000333 0.000000

PWB6K E= -39.854636
C 0.000000 0.000294 0.000000
H 0.000000 -0.002977 0.000000
H -0.002231 0.001342 0.000000
H 0.002231 0.001342 0.000000

SOGGA E= -39.538835
C 0.000000 0.000313 0.000000
H 0.000000 0.011083 0.000000
H 0.009947 -0.005698 0.000000
H -0.009947 -0.005698 0.000000

SOGGA11 E= -39.842525
C 0.000000 0.000229 0.000000
H 0.000000 0.006611 0.000000
H 0.006004 -0.003420 0.000000
H -0.006004 -0.003420 0.000000

SOGGA11-X E= -39.831323
C 0.000000 0.000292 0.000000
H 0.000000 0.003387 0.000000
H 0.003276 -0.001840 0.000000

 10

H -0.003276 -0.001840 0.000000

N12 E= -39.822945
C 0.000000 0.000149 0.000000
H 0.000000 -0.000495 0.000000
H -0.000108 0.000173 0.000000
H 0.000108 0.000173 0.000000

N12-SX E= -39.823220
C 0.000000 0.000282 0.000000
H 0.000000 -0.002663 0.000000
H -0.001970 0.001191 0.000000
H 0.001970 0.001191 0.000000

M08-HX E= -39.828570
C 0.000000 0.000294 0.000000
H 0.000000 0.003959 0.000000
H 0.003782 -0.002126 0.000000
H -0.003782 -0.002126 0.000000

M11 E= -39.805603
C 0.000000 0.000277 0.000000
H 0.000000 0.005260 0.000000
H 0.004876 -0.002769 0.000000
H -0.004876 -0.002769 0.000000

M11-L E= -39.827503
C 0.000000 0.000257 0.000000
H 0.000000 0.004995 0.000000
H 0.004663 -0.002626 0.000000
H -0.004663 -0.002626 0.000000

MN12-L E= -39.776262
C 0.000000 0.000205 0.000000
H 0.000000 0.001150 0.000000
H 0.001371 -0.000678 0.000000
H 0.001371 -0.000678 0.000000

MN12-SX E= -39.802089
C 0.000000 0.000233 0.000000
H 0.000000 0.001712 0.000000
H 0.001846 -0.000972 0.000000
H -0.001846 -0.000972 0.000000

GAM E= -39.857257
C 0.000000 0.000306 0.000000

 11

H 0.000000 0.000744 0.000000

H 0.000994 -0.000525 0.000000
H -0.000994 -0.000525 0.000000

MN15-L E= -39.790513
C 0.000000 0.000313 0.000000
H 0.000000 0.008751 0.000000
H 0.007937 -0.004532 0.000000
H -0.007937 -0.004532 0.000000

MN15 E= -39.780507
C 0.000000 0.000300 0.000000
H 0.000000 0.001890 0.000000
H 0.001985 -0.001095 0.000000
H -0.001985 -0.001095 0.000000

PBEsol E= -39.586795
C 0.000000 0.000311 0.000000
H 0.000000 0.010513 0.000000
H 0.009453 -0.005412 0.000000
H -0.009453 -0.005412 0.000000

WC06 E= -39.673096
C 0.000000 0.000307 0.000000
H 0.000000 0.008746 0.000000
H 0.007921 -0.004527 0.000000
H -0.007921 -0.004527 0.000000

RPBE E= -39.847464
C 0.000000 0.000305 0.000000
H 0.000000 0.008991 0.000000
H 0.008133 -0.004648 0.000000
H -0.008133 -0.004648 0.000000

revPBE E= -39.831098
C 0.000000 0.000305 0.000000
H 0.000000 0.008874 0.000000
H 0.008032 -0.004590 0.000000
H -0.008032 -0.004590 0.000000

B97-3 E= -39.833716
C 0.000000 0.000300 0.000000
H 0.000000 0.002450 0.000000
H 0.002469 -0.001375 0.000000
H -0.002469 -0.001375 0.000000

 12

Geometries of H2O (in angstrom)

*****************************************************
O 0.000000 0.000000 0.000000
H 0.000000 0.000000 0.956914
H 0.926363 0.000000 -0.239868
*****************************************************

Table 4. Reference energies (Eh) and forces (X,Y,Z, Eh/a0) for H2O
M06 E= -76.397702
O -0.002239 0.000000 -0.001733
H -0.002242 0.000000 0.005209
H 0.004481 0.000000 -0.003476

M06-L E= -76.420152
O -0.002994 0.000000 -0.002317
H -0.000683 0.000000 0.003975
H 0.003677 0.000000 -0.001658

M06-2X E= -76.394863
O -0.002361 0.000000 -0.001828
H -0.002678 0.000000 0.005899
H 0.005039 0.000000 -0.004072

M06-HF E= -76.391767
O 0.000348 0.000000 0.000270
H -0.005141 0.000000 0.006282
H 0.004793 0.000000 -0.006551

M05-2X E= -76.416245
O -0.000061 0.000000 -0.000047
H -0.002966 0.000000 0.003895
H 0.003027 0.000000 -0.003848

M05 E= -76.398883
O -0.001497 0.000000 -0.001159
H -0.001588 0.000000 0.003598
H 0.003085 0.000000 -0.002439

M08-HX E= -76.397793
O -0.000086 0.000000 -0.000067
H -0.003293 0.000000 0.004343
H 0.003379 0.000000 -0.004276

 13

M08-SO E= -76.381535
O -0.005417 0.000000 -0.004193
H -0.003612 0.000000 0.010262
H 0.009029 0.000000 -0.006069

M11 E= -76.403933
O -0.001641 0.000000 -0.001270
H -0.003892 0.000000 0.006723
H 0.005533 0.000000 -0.005453

M11-L E= -76.404506
O 0.003288 0.000000 0.002545
H -0.000043 0.000000 -0.003341
H -0.003245 0.000000 0.000795

MN12-L E= -76.355836
O 0.001127 0.000000 0.000873
H -0.003229 0.000000 0.003006
H 0.002101 0.000000 -0.003879

MN12-SX E= -76.373687
O -0.003107 0.000000 -0.002405
H -0.003170 0.000000 0.007304
H 0.006277 0.000000 -0.004900

SOGGA11 E= -76.423371
O -0.003780 0.000000 -0.002926
H -0.000816 0.000000 0.004959
H 0.004596 0.000000 -0.002033

SOGGA11-X E= -76.405420
O -0.000473 0.000000 -0.000366
H -0.001773 0.000000 0.002779
H 0.002246 0.000000 -0.002413

N12 E= -76.383122
O 0.003850 0.000000 0.002980
H -0.002507 0.000000 -0.000738
H -0.001343 0.000000 -0.002242

N12-SX E= -76.385858
O 0.003032 0.000000 0.002347
H -0.003636 0.000000 0.001566
H 0.000604 0.000000 -0.003913

GAM E= -76.402043

 14

O 0.003354 0.000000 0.002596

H -0.000553 0.000000 -0.002749
H -0.002800 0.000000 0.000154

MN15-L E= -76.347439
O -0.006624 0.000000 -0.005128
H -0.000844 0.000000 0.007933
H 0.007468 0.000000 -0.002805

MN15 E= -76.351267
O -0.005094 0.000000 -0.003943
H -0.003620 0.000000 0.009939
H 0.008715 0.000000 -0.005996

M08-HX E= -76.132125
Exchange-only with O -0.011250 0.000000 -0.008708
0.5223EHFE included H -0.003871 0.000000 0.016623
H 0.015122 0.000000 -0.007915

M08-HX E= -72.106719
Correlation and 0.5223EHFE O -0.101534 0.000000 -0.078592
only (no meta exchange) H -0.005570 0.000000 0.112079
H 0.107104 0.000000 -0.033487

M08-HX E= -67.697943
Correlation-only with O -0.234053 0.000000 -0.181167
no meta or HF exchange H -0.010609 0.000000 0.255477
H 0.244661 0.000000 -0.074310

Note: the final three entries in the above table are for developers.

 15

Version history
Version 1, December 31, 2008
Original version

Version 1.1, April 23, 2009

Added SOGGA

Version 1.2, May 14, 2009

Fixed some bugs, added reference energies and forces in the manual

Version 1.3, May 12, 2011

Added SOGGA11

Version 1.4 October 07, 2011

Fixed some bugs, added reference citation for SOGGA11.

Version 1.5 November 07, 2011

Added SOGGA11-X and M11

Version 1.6 December 05, 2011

Added M11-L, fixed some bugs

Version 1.7 April 18, 2012

Added N12, fixed some bugs

Version 1.8 September 05, 2012

Added MN12-L, N12-SX, and MN12-SX, fixed some bugs

Version 2.0 January 27, 2016

Added GAM, MN15-L, and MN15