SSUMES reference manual

files created in the current directory:

mas1t.dat
ratout.dat
ratout.csv
ratnum.csv
tunnel.dat

The rrkmth program is a modified version of RRKM program in the UNIMOL suite. In the SSUMES, this program is mainly used to generates a MASTER input file containing density of states, ρ(E), of the molecule and microscopic rate coefficients, k(E), of the dissociation and/or isomerization channels, though it is also capable of calculating tranditional RRKM calculations for strong-collision limit, etc.

Part of the sample RRKM input file, rc2h2ph_s_rrkm.inp, is shown below.

phenylc2h2 2-channel (ch3-ch*,ch4-cc*) simple mode… ·· 1    TITLE
 700 100  7 6  2  0                                 ·· 2   NN,INC,NP,NT,NCHAN,JAV
 37 37 39                                           ·· 11n (JF(IN),IN=1,NCHAN),NF
 36.290 43.135                                      ·· 12n E0K(IN),IN=1,NCHAN
 1 1 1                                              ·· 13n (SRC(IN),IN=1,NCHAN),SRM
 -0.0447110 -0.0379942 -0.0465263                   ·· 14n (BCMPLX(IN),IN=1,NCHAN),BMOLEC
 2 2 1                                              ·· 15n (N(IN),IN=1,NCHAN),NINTR
 0.1798986 1 1 0 0                                  ·· 16n (BVEC(IN,J),SIGVC(IN,J),IRTDMC(IN,J),HOHNDC(IN,J),V0C(IN,J),J=1,N(IN))
 3.4560830 2 1 55 130                                   :
 0.1649022 1 1 0 0                                      :
 1.3610300 2 1 12 80                                    :
 0.1768391 1 1 0 0                                  ·· 17n BVECM(J),SIGVCM(J),IRTDMM(J),HOHNDM(J),V0M(J),J=1,NINTR
 4.240 103.054775 28.013400 271.0                   ·· 18n SGMA,WT1,WT2,EPS
 149 1                                              ·· 21n NC(IN,I),JC(IN,I),I=1,JF(IN)
 213 1                                                  :
  :                                                   (snip)
 3381 1                                                 :
 83 1                                               ·· 22n NM(I),JM(I),I=1,NF
 210 1                                                  :
  :                                                   (snip)
 3154 1                                                 :
 76. 760. 7.6E+3 7.6E+4 7.6E+8 7.6E+11 7.6E+14      ·· 26  PRESS(I),I=1,NP
 2000.000 1000.000 666.667 500.000 400.000 300.000  ·· 27  TEMP(I),I=1,NT
 1 1                                                ·· 28  ITPTUN(IN),IN=1,NCHAN
 30.195 694 1                                       ·· 29  DELTAH(IN),FRQIMG(IN),RDMIRC(IN),IN=1,NCHAN
 40.528 314 1                                           :
 1 1 1                                              ·· 30  (NCNFC(IN),IN=1,NCHAN),NCNFM
  1 0                                               ·· 31  JCNFC(IN,I),ECNFC(IN,I),I=1,NCNFC(IN)
  1 0                                                   :
  1 0                                               ·· 32  JCNFM(I),ECNFM(I),I=1,NCNFM

1.	TITLE
		Title; up to 80 characters.
2.	NN,INC,NP,NT,NCHAN,JAV
		NN: no. of energy increments to be used; INC: integration increment in cm⁻¹; usually 100 cm⁻¹; NP: no. of input pressures; NT: no. of input temperatures; NCHAN: no. of reaction channels (up tp 7); may be increased by re-compiling JAV: should be always 0.
11n.	(JF(IN), IN=1,NCHAN ),NF
		JF(IN): number of distinct frequencies in transition state for channel IN; NF: number of distinct frequencies in reactant molecule.
12n.	E0K(IN), IN=1,NCHAN
		critical energy E₀ (kcal mol⁻¹) for each channel. Must be in increasing order.
13n.	(SRC(IN), IN=1,NCHAN ),SRM
		SRC(IN): σ/n for IN^th activated complex (σ =symmetry number; n = no. of optical isomers); SRM: same, for reactant.
14n.	(BCMPLX(IN), IN=1,NCHAN ),BMOLEC
		BCMPLX(IN): rotational constant* (cm⁻¹) for inactive external rotations for IN^th activated complex; BMOLEC: same for reactant. * If input as negative number, it is considered as a two-dimensional rotor.
15n.	(N(IN), IN=1,NCHAN ),NINTR
		N(IN): no. of active rotations (internal plus external) in INth activated complex; if input as negative number, implies linear activated complex. Either free or hindered rotor treatment for 1-dimentional rotor is possible. NINTR: same for reactant.
- Input no. 16n looped through IN = 1,NCHAN
16n.	(only present if N(IN) > 0) (BVEC(IN,J),SIGVC(IN,J),IRTDMC(IN,J),HOHNDC(IN,J),V0C(IN,J), J=1,N(IN) )
		for J^th active rotation of IN^th activated complex: BVEC(IN,J): rotational constant (cm⁻¹); SIGVC(IN,J): σ/n; IRTDMC(IN,J): dimension; HOHNDC(IN,J): harmonic oscillator frequency^# (cm⁻¹) of hindered rotor; For free rotor, set this value to zero. If this set > 0, the rotor is always treated as 1-dimensional irrespective of the IRTDMC(IN,J) input. V0C(IN,J): barrier height^# of the symmetric internal-rotation potential; This is not used when HOHNDC(IN,J) = 0. If V0C(IN,J) < 0, the barrier height is calculated from BVEC, SIGVC, and HOHNDC. It should be noted that, when V0C(IN,J) = 0 and HOHNDC(IN,J) > 0, it is treaded as a free rotor but the loss of the zero-point energy was corrected by using HOHNDC(IN,J). When HOHNDC(IN,J) = 0, this correction will not be done. ^# Note that the density of state is divided by SIGVC(IN,J). If this is used as the approximate symmetry number of the rotation potential, correction must be given in SRC(IN). For example for a -CXYZ rotor, potential may be approximated by three-fold symmetry and SIGVC(IN,J) may be set to three, but, since it is not really three-fold symmetric as -CH₃ rotor, SRC(IN) must be divided by three to compensate this artificial symmetry number.
17n.	(only present if NINTR > 0) BVECM(J),SIGVCM(J),IRTDMM(J),HOHNDM(J),V0M(J), J=1,NINTR
		as in input 16n, except for J^th active rotation of reactant.
18n.	SGMA,WT1,WT2,EPS
		SGMA: hard-sphere or Lennard-Jones diameter (Å) for reactant-bath-gas interaction, for calculating ω; WT1: molecular weight of reactant (a.m.u.). If negative and JAV ≠ 0 then used as a flag for entering a range of inactive two-dimensional external rotational constants vs breaking bond length, this option should be used if the centre of mass of at least one of the fragments does not coincide with the pivot atom of that fragment; WT2: molecular weight of bath gas (a.m.u.); EPS: if negative, flag for using hard-sphere collision frequency; if positive, Lennard-Jones well depth ε (K), for calculating ω.
- Input no. 21n looped through IN = 1,NCHAN
21n.	NC(IN,I),JC(IN,I), I=1,JF(IN)
		NC(IN,I): vibrational frequency (cm⁻¹) of I^th oscillator of IN^th activated complex; JC(IN,I): degeneracy of I^th oscillator of IN^th activated complex.
22n.	NM(I),JM(I), I=1,NF
		as in input no. 21n, for reactant.
26.	PRESS(I), I=1,NP
		list of pressures (torr).
27.	TEMP(I), I=1,NT
		list of temperatures (K); must be in decreasing order.
- Followings are optional. If input 28 is not found, no tunneling treatment nor rotational-conformer treatment is done.
28.	ITPTUN(IN), IN=1,NCHAN
		flag for tunneling treatment : 0..no tunneling treatment, 1..Eckart tunneling treatment.
29.	(present only if ITPTUN(IN)=1) DELTAH(IN), FRQIMG(IN), RDMIRC(IN), IN=1,NCHAN
		DELTAH(IN): heat of reaction at 0 K for channel IN (kcal mol⁻¹); FRQIMG(IN): modulus of the imaginary frequency, ν^‡, at the top of the barrier along IRC (cm⁻¹); enter modulus (absolute value), \|ν^‡\|, i.e., positive real value. RDMIRC(IN): reduced mass along the IRC* (a.m.u.); * This parameter does not affect the results of the calculation, but only affect the diagnostic output, k[N/m] and alpha[/m], in "tunnel.dat". Give an arbitrary value around 1.0 if you do not care about these outputs.
- Followings are optional. If input 30 is not found, no rotational-conformer treatment is done. Input 28 must present when input 30 is given.
30.	(NCNFC(IN), IN=1,NCHAN ),NCNFM
		NCNFC(IN) : number of the rotational conformers* of IN^th activated complex including the ground-state conformer; NCNFM : number of the rotational conformers* of the reactant including the ground-state conformer. * NCNFM=0 is equivalent to NCNFM=1, JCNFM(1)=1, and ECNFM(1)=0. The behavior is similar for NCNFC(IN)=0.
- Input no. 31 looped through IN = 1,NCHAN
31.	(present only if NCNFC(IN) > 0) JCNFC(IN,I), ECNFC(IN,I), I=1,NCNFC(IN)
		for I^th rotational conformer of IN^th activated complex: JCNFC(IN,I): degeneracy* of the conformer; ECNFC(IN,I): energy^# of the conformer (cm⁻¹). * It should be noted that the SRC(IN) (σ/n) in input 13n applies all the rotational conformers, and the degeneracy for the conformer should not be duplicated in SRC(IN) and JCNFC(IN,I) here. ^# Do not forget to include the ground-state conformer. That is, the first record should be the ground state with energy 0.
32.	(present only if NCNFM > 0) JCNFM(I),ECNFM(I), I=1,NCNFM
		as in input 31, except for I^th rotational conformer of the reactant.

The main comprehensive output is made to the console and can be stored to a file by redirection. Summary of the high-pressure limiting rate coefficients calculated from thermodynamics is written to ratout.dat and ratout.csv. High-pressure limiting rate coefficients calculated by numerical integration are written to ratnum.csv. The MASTER file with fixed file name, mas1t.dat, for ssumes programs and mas55c3 is also created. Informations on the tunneling calculations are written in tunnel.dat.