MC-PDFT in GAMESS

Multiconfiguration Pair-Density Functional Theory (MC-PDFT) is available in the new version of GAMESS released on Sept. 30, 2019. It can be downloaded at (https://www.msg.chem.iastate.edu/gamess/download.html).

• MC-PDFT [1,2] combines multiconfiguration self-consistent field (MCSCF) and density functional approaches. In MC-PDFT, an MCSCF wave function is used to calculate the kinetic energy, electron nuclear attraction, and the classical electron-electron repulsion contributions to the total energy. The remaining energy comes from an on-top density functional.
  [1] “Multiconfiguration Pair-Density Functional Theory," G. Li Manni, R. K. Carlson, S. Luo, D. Ma, J. Olsen, D. G. Truhlar, and L. Gagliardi, Journal of Chemical Theory and Computation 10, 3669-3680 (2014). doi.org/10.1021/ct500483t
  [2] "Multiconfiguration Pair-Density Functional Theory: A New Way to Treat Strongly Correlated Systems," L. Gagliardi, D. G. Truhlar, G. Li Manni, R. K. Carlson, C. E. Hoyer, and J. L. Bao, Accounts of Chemical Research 50, 66-73 (2017). doi.org/10.1021/acs.accounts.6b00471
• MC-PDFT is implemented now only for the ALDET CI option. This means it can be used with CASSCF (also called FORS) but not (at the present time) with ORMAS.
• MC-PDFT calculations can be done by specifying SCFTYP=MCSCF and PDFTYP=MC-PDFT functional
• Keywords for available MC-PDFT functionals:
  

  Functional	Keyword
  tPBE	PDFTYP=TPBE
  ftPBE	PDFTYP=FTPBE
  tBLYP	PDFTYP=TBLYP
  ftBLYP	PDFTYP=FTBLYP
  trevPBE	PDFTYP=TREVPBE
  ftrevPBE	PDFTYP=FTREVPBE

  
  
• The current implementation works for single-point ground state calculations and for state-specific and state-averaged excited states. (Analytic MC-PDFT gradients are not yet available in GAMESS.)

Sample input file for a single point MC-PDFT calculation for the water molecule.

$CONTRL SCFTYP=MCSCF PDFTYP=TPBE $END
 $SYSTEM TIMLIM=1 $END
 $BASIS  GBASIS=N21 NGAUSS=3 $END
 $MCSCF CISTEP=ALDET CANONC=.false. $END
---- EXPERIMENTAL GEOM, R(OH)=0.95781A, HOH=104.4776 DEG.
 $DATA
WATER...3-21G BASIS...FORS-MCSCF...EXPERIMENTAL GEOMETRY
Cnv 2

Oxygen     8.0
Hydrogen   1.0   0.0   0.7572157   0.5865358
 $END
 $GUESS  GUESS=MOREAD  NORB=13 $END
 $DET NSTATE=1 NCORE=0 NACT=7 NELS=10
 ANALYS=.false. $END

---- CONVERGED 3-21G WATER VECTORS, E=-75.585409913 -----
 $VEC
 1  1 0.98323195E+00 0.95883436E-01 0.00000000E+00 0.00000000E+00 0.35370268E-02
 1  2-0.38015713E-01 0.00000000E+00 0.00000000E+00-0.67933232E-02 0.26157699E-02
 1  3 0.69075022E-02 0.26157699E-02 0.69075022E-02
 2  1-0.22915183E+00 0.21751680E+00 0.00000000E+00 0.00000000E+00 0.83482416E-01
 2  2 0.70627255E+00 0.00000000E+00 0.00000000E+00 0.93448600E-01 0.11715069E+00
 2  3 0.19083329E-01 0.11715069E+00 0.19083329E-01
 3  1 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.39852684E+00 0.00000000E+00
 3  2 0.00000000E+00 0.00000000E+00 0.36975524E+00 0.00000000E+00-0.23386378E+00
 3  3-0.18332401E+00 0.23386378E+00 0.18332401E+00
 4  1-0.88424758E-01 0.82203534E-01 0.00000000E+00 0.00000000E+00-0.44197156E+00
 4  2 0.40499817E+00 0.00000000E+00 0.00000000E+00-0.50792220E+00-0.13089427E+00
 4  3-0.10523065E+00-0.13089427E+00-0.10523065E+00
 5  1 0.00000000E+00 0.00000000E+00 0.52129122E+00 0.00000000E+00 0.00000000E+00
 5  2 0.00000000E+00 0.63210541E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00
 5  3 0.00000000E+00 0.00000000E+00 0.00000000E+00
 6  1-0.10921346E+00 0.34847757E-01 0.00000000E+00 0.00000000E+00 0.20920102E+00
 6  2 0.10449784E+01 0.00000000E+00 0.00000000E+00 0.46616469E+00-0.46425782E-01
 6  3-0.86310980E+00-0.46425782E-01-0.86310980E+00
 7  1 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.30311516E+00 0.00000000E+00
 7  2 0.00000000E+00 0.00000000E+00 0.77474462E+00 0.00000000E+00 0.36159920E-01
 7  3 0.11766731E+01-0.36159920E-01-0.11766731E+01
 8  1 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.18247792E+00 0.00000000E+00
 8  2 0.00000000E+00 0.00000000E+00 0.45271854E+00 0.00000000E+00 0.96497497E+00
 8  3-0.68407554E+00-0.96497497E+00 0.68407554E+00
 9  1-0.68462918E-01 0.98778424E-01 0.00000000E+00 0.00000000E+00 0.27668306E+00
 9  2 0.11645921E+00 0.00000000E+00 0.00000000E+00 0.30171282E+00-0.98500862E+00
 9  3 0.48555609E+00-0.98500862E+00 0.48555609E+00
10  1 0.00000000E+00 0.00000000E+00 0.10292728E+01 0.00000000E+00 0.00000000E+00
10  2 0.00000000E+00-0.96518900E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00
10  3 0.00000000E+00 0.00000000E+00 0.00000000E+00
11  1-0.45193228E-01 0.13566837E+00 0.00000000E+00 0.00000000E+00-0.10100340E+01
11  2 0.17234151E+00 0.00000000E+00 0.00000000E+00 0.11527420E+01-0.26046385E+00
11  3-0.92175886E-01-0.26046385E+00-0.92175886E-01
12  1 0.00000000E+00 0.00000000E+00 0.00000000E+00-0.10670424E+01 0.00000000E+00
12  2 0.00000000E+00 0.00000000E+00 0.13962359E+01 0.00000000E+00 0.13746917E+00
12  3 0.50761817E+00-0.13746917E+00-0.50761817E+00
13  1-0.84642669E-01 0.16413752E+01 0.00000000E+00 0.00000000E+00 0.16053837E+00
13  2-0.19938626E+01 0.00000000E+00 0.00000000E+00-0.49752222E+00 0.28728587E+00
13  3 0.35961579E+00 0.28728587E+00 0.35961579E+00
 $END

Credits

Incorporation of MC-PDFT in the Sept. 30, 2019 version of GAMESS is primarily the work of Prachi Sharma.

Links to Other Pages of Interest:

Laura Gagliardi Group Homepage
Don Truhlar Group Homepage
Gagliardi Group Software page
Truhlar Group Software page
Chemical Theory Center at the University of Minnesota
Department of Chemistry at the University of Minnesota