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<p><span style="font-size:12pt">Hello Molpro users/developers,</span></p>
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<p style="font-family:Calibri,Arial,Helvetica,sans-serif; font-size:16px"><strong>Summary</strong>: When out-of-plane constraint angles are specified in radians and the unit is explicitly stated, Molpro incorrectly multiplies the input angle by 1/0.529, the
Angstrom-to-Bohr conversion factor. <span style="font-size:12pt">Additionally, when the unit is left out, Molpro interprets angles as being in radians, in contradiction to the documentation (</span><span style="font-size:12pt">https://www.molpro.net/info/2015.1/doc/manual/node645.html</span><span style="font-size:12pt">) </span></p>
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I am running three calculations, where everything is held constant except the units in the constraint line. Here are three variations:<br>
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<div style="margin:0px; padding:0px">{optg,maxit=50</div>
<div style="margin:0px; padding:0px">method,slrf</div>
<div style="margin:0px; padding:0px">constraint,-0.226874,outofplane,atoms=[7,6,8,9]</div>
<div style="margin:0px; padding:0px">}</div>
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{optg,maxit=50</div>
<div style="margin:0px; padding:0px">method,slrf</div>
<div style="margin:0px; padding:0px">constraint,-0.226874,deg,outofplane,atoms=[7,6,8,9]</div>
<div style="margin:0px; padding:0px">}</div>
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{optg,maxit=50</div>
<div style="margin:0px; padding:0px">method,slrf</div>
<div style="margin:0px; padding:0px">constraint,-0.226874,rad,outofplane,atoms=[7,6,8,9]<br>
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<div style="margin:0px; padding:0px">}</div>
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<div style="margin:0px; padding:0px">Here is how molpro interprets these three conditions:</div>
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<div style="margin:0px; padding:0px"><strong>CONDITION 1: </strong></div>
<div style="margin:0px; padding:0px"><span style="background-color:transparent"><strong>{optg,maxit=50</strong></span></div>
<div style="margin:0px; padding:0px"><strong>method,slrf</strong></div>
<div style="margin:0px; padding:0px"><strong>constraint,-0.226874,outofplane,atoms=[7,6,8,9]</strong></div>
<div style="margin:0px; padding:0px"><strong>}</strong></div>
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<div style="margin:0px; padding:0px">
<div style="margin:0px; padding:0px">********** USER DEFINED INT/FIX/CONSTRAINTS ****************</div>
<div style="margin:0px; padding:0px"><br>
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<div style="margin:0px; padding:0px">List of primitive internal coordinates</div>
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<div style="margin:0px; padding:0px"> N Name Type Natoms Atom list</div>
<div style="margin:0px; padding:0px"><br>
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<div style="margin:0px; padding:0px"> 1 Ou0001 OutOfP 4 N6 C5 O7 O8 </div>
<div style="margin:0px; padding:0px"><br>
</div>
<div style="margin:0px; padding:0px">List of user defined internal/fixed coordinates and constraints</div>
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<div style="margin:0px; padding:0px">- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - </div>
<div style="margin:0px; padding:0px"> N Name Type Pname Coeff Value Unit</div>
<div style="margin:0px; padding:0px">- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - </div>
<div style="margin:0px; padding:0px"> 1 Cns001 Con Ou0001 1.000 -0.22687 Bohr</div>
<div style="margin:0px; padding:0px">- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - </div>
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<div style="margin:0px; padding:0px">******************************************************************</div>
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<div style="margin:0px; padding:0px">************************************************************************************************************************</div>
<div style="margin:0px; padding:0px">OU0001 = OUTOFP N6 C5 O7 O8</div>
<div style="margin:0px; padding:0px">VALUES</div>
<div style="margin:0px; padding:0px">OU0001 = -0.22687400</div>
<div style="margin:0px; padding:0px">************************************************************************************************************************</div>
<div style="margin:0px; padding:0px"> </div>
<div style="margin:0px; padding:0px"> </div>
<div style="margin:0px; padding:0px"> *************************************************************</div>
<div style="margin:0px; padding:0px"> * Values of the primitive constraints *</div>
<div style="margin:0px; padding:0px"> *************************************************************</div>
<div style="margin:0px; padding:0px"> OU0001 : Out of plane angle= 0.0011/degree, 0.0000/rad</div>
<div style="margin:0px; padding:0px"> </div>
<div style="margin:0px; padding:0px"> *******************************************</div>
<div style="margin:0px; padding:0px"> * Values of the constraints / au or rad *</div>
<div style="margin:0px; padding:0px"> *******************************************</div>
<div style="margin:0px; padding:0px"> Label C C0</div>
<div style="margin:0px; padding:0px"> Cns001 0.000019 -0.226874</div>
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<strong>CONDITION 2:</strong></div>
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<div style="margin:0px; padding:0px"><strong>{optg,maxit=50</strong></div>
<div style="margin:0px; padding:0px"><strong>method,slrf</strong></div>
<div style="margin:0px; padding:0px"><strong>constraint,-0.226874,deg,outofplane,atoms=[7,6,8,9]</strong></div>
<div style="margin:0px; padding:0px"><strong>}</strong></div>
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<div style="margin:0px; padding:0px">********** USER DEFINED INT/FIX/CONSTRAINTS ****************</div>
<div style="margin:0px; padding:0px"><br>
</div>
<div style="margin:0px; padding:0px">List of primitive internal coordinates</div>
<div style="margin:0px; padding:0px"><br>
</div>
<div style="margin:0px; padding:0px"> N Name Type Natoms Atom list</div>
<div style="margin:0px; padding:0px"><br>
</div>
<div style="margin:0px; padding:0px"> 1 Ou0001 OutOfP 4 N6 C5 O7 O8 </div>
<div style="margin:0px; padding:0px"><br>
</div>
<div style="margin:0px; padding:0px">List of user defined internal/fixed coordinates and constraints</div>
<div style="margin:0px; padding:0px"><br>
</div>
<div style="margin:0px; padding:0px">- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - </div>
<div style="margin:0px; padding:0px"> N Name Type Pname Coeff Value Unit</div>
<div style="margin:0px; padding:0px">- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - </div>
<div style="margin:0px; padding:0px"> 1 Cns001 Con Ou0001 1.000 -0.22687 Bohr</div>
<div style="margin:0px; padding:0px">- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - <br>
</div>
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<div style="margin:0px; padding:0px">OU0001 = OUTOFP N6 C5 O7 O8</div>
<div style="margin:0px; padding:0px">VALUES</div>
<div style="margin:0px; padding:0px">OU0001 = -0.22687400</div>
<div style="margin:0px; padding:0px">************************************************************************************************************************</div>
<div style="margin:0px; padding:0px"> </div>
<div style="margin:0px; padding:0px"> </div>
<div style="margin:0px; padding:0px"> *************************************************************</div>
<div style="margin:0px; padding:0px"> * Values of the primitive constraints *</div>
<div style="margin:0px; padding:0px"> *************************************************************</div>
<div style="margin:0px; padding:0px"> OU0001 : Out of plane angle= 0.0011/degree, 0.0000/rad</div>
<div style="margin:0px; padding:0px"> </div>
<div style="margin:0px; padding:0px"> *******************************************</div>
<div style="margin:0px; padding:0px"> * Values of the constraints / au or rad *</div>
<div style="margin:0px; padding:0px"> *******************************************</div>
<div style="margin:0px; padding:0px"> Label C C0</div>
<div style="margin:0px; padding:0px"> Cns001 0.000019 -0.226874</div>
</div>
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<strong>CONDITION 3:</strong></div>
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<div style="margin:0px; padding:0px"><strong>{optg,maxit=50</strong></div>
<div style="margin:0px; padding:0px"><strong>method,slrf</strong></div>
<div style="margin:0px; padding:0px"><strong>constraint,-0.226874,rad,outofplane,atoms=[7,6,8,9]</strong></div>
<div style="margin:0px; padding:0px"><strong>}</strong></div>
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<div style="background-color:rgb(255,255,255); margin:0px; padding:0px; font-family:Consolas,"Courier New",monospace; font-size:14.634px">
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<div style="margin:0px; padding:0px">********** USER DEFINED INT/FIX/CONSTRAINTS ****************</div>
<div style="margin:0px; padding:0px"><br>
</div>
<div style="margin:0px; padding:0px">List of primitive internal coordinates</div>
<div style="margin:0px; padding:0px"><br>
</div>
<div style="margin:0px; padding:0px"> N Name Type Natoms Atom list</div>
<div style="margin:0px; padding:0px"><br>
</div>
<div style="margin:0px; padding:0px"> 1 Ou0001 OutOfP 4 N6 C5 O7 O8 </div>
<div style="margin:0px; padding:0px"><br>
</div>
<div style="margin:0px; padding:0px">List of user defined internal/fixed coordinates and constraints</div>
<div style="margin:0px; padding:0px"><br>
</div>
<div style="margin:0px; padding:0px">- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - </div>
<div style="margin:0px; padding:0px"> N Name Type Pname Coeff Value Unit</div>
<div style="margin:0px; padding:0px">- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - </div>
<div style="margin:0px; padding:0px"> 1 Cns001 Con Ou0001 1.000 -0.22687 Angstrom</div>
<div style="margin:0px; padding:0px">- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - <br>
</div>
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</div>
<div style="margin:0px; padding:0px">OU0001 = OUTOFP N6 C5 O7 O8</div>
<div style="margin:0px; padding:0px">VALUES</div>
<div style="margin:0px; padding:0px">OU0001 = -0.22687400 ANGSTROM</div>
<div style="margin:0px; padding:0px">************************************************************************************************************************</div>
<div style="margin:0px; padding:0px"> </div>
<div style="margin:0px; padding:0px"> </div>
<div style="margin:0px; padding:0px"> *************************************************************</div>
<div style="margin:0px; padding:0px"> * Values of the primitive constraints *</div>
<div style="margin:0px; padding:0px"> *************************************************************</div>
<div style="margin:0px; padding:0px"> OU0001 : Out of plane angle= 0.0011/degree, 0.0000/rad</div>
<div style="margin:0px; padding:0px"> </div>
<div style="margin:0px; padding:0px"> *******************************************</div>
<div style="margin:0px; padding:0px"> * Values of the constraints / au or rad *</div>
<div style="margin:0px; padding:0px"> *******************************************</div>
<div style="margin:0px; padding:0px"> Label C C0</div>
<div style="margin:0px; padding:0px"> Cns001 0.000019 -0.428730<br>
</div>
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</div>
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<div style="margin:0px; padding:0px; font-size:14.634px">So when no units are specified, molpro took the constraint to be -0.227 <strong>BOHRS </strong>(???) but then later also prints that it is -0.227 radians. </div>
<div style="margin:0px; padding:0px; font-size:14.634px"><br>
</div>
<div style="margin:0px; padding:0px; font-size:14.634px">Okay, at this point I'm thinking "They have a silly little printing bug; they have quantities in either bohrs/radians or angstroms/degrees, and printed BOHR instead of RADIAN to mean that we're in the
first regime."<br>
</div>
<div style="margin:0px; padding:0px; font-size:14.634px"><br>
</div>
<div style="margin:0px; padding:0px; font-size:14.634px">But when degrees were specified, molpro again states that the constraint is -0.227 BOHRS, then prints -0.227 radians.</div>
<div style="margin:0px; padding:0px; font-size:14.634px"><br>
</div>
<div style="margin:0px; padding:0px; font-size:14.634px">So now I'm thinking, "It just ignores the units on the constraint." Fine.</div>
<div style="margin:0px; padding:0px; font-size:14.634px"><br>
</div>
<div style="margin:0px; padding:0px; font-size:14.634px">But in condition 3 (input says radians), we have <span style="background-color:transparent">-0.22687 <strong>Angstrom</strong> and the constraint value later printed as </span><span style="background-color:transparent">-0.428730 <strong>radians</strong>.</span></div>
<div style="margin:0px; padding:0px; font-size:14.634px"><span style="background-color:transparent"><br>
</span></div>
<div style="margin:0px; padding:0px; font-size:14.634px">So the unit on the constraint is not being ignored. Even worse, that -0.42873 is suspiciously like 2 * -0.227, or more precisely 1/0.529 * -0.227.</div>
<div style="margin:0px; padding:0px; font-size:14.634px"><br>
</div>
<div style="margin:0px; padding:0px; font-size:14.634px">In other words, <strong>molpro went and converted my radians into radians as if it were converting angstrom to bohrs.</strong></div>
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</strong></div>
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</strong></div>
<div style="margin:0px; padding:0px; font-size:14.634px"><strong>Full input</strong>:<br>
</div>
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</div>
<div style="margin:0px; padding:0px; font-size:14.634px">(You will probably need to replace the basis=desavdz-rev5 with some other basis to run this.)<br>
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<div>***,nitrobenzene</div>
<div>memory,925,M<br>
</div>
<div>gdirect</div>
<div>thrdscf=1e-12,thrdscf_max=1e-9</div>
<div>gthresh,throvl=1e-9,throrth=1e-7,energy=1e-8,optgrad=1e-4,optstep=1e-4,optenerg=1e-6</div>
<div>set,charge=0</div>
<div>set,spin=0</div>
<div>geomtyp=xyz</div>
<div>symmetry,nosym</div>
<div>orient,noorient</div>
<div>geometry=</div>
<div>{</div>
<div>14</div>
<div>No title</div>
<div>C0 1.8842800000 -1.0404400000 -0.1298200000</div>
<div>C1 0.8050200000 -0.4387900000 0.5477900000</div>
<div>C2 2.9451500000 -1.6111600000 0.6014600000</div>
<div>C3 0.7763200000 -0.4020600000 1.9543900000</div>
<div>C4 2.9373100000 -1.5857400000 2.0085900000</div>
<div>C5 1.8480500000 -0.9790600000 2.6553800000</div>
<div>N6 1.8287700000 -0.9463200000 4.1392300000</div>
<div>O7 0.8566600000 -0.4084700000 4.6891700000</div>
<div>O8 2.7859900000 -1.4587800000 4.7374200000</div>
<div>H9 1.8984500000 -1.0646300000 -1.2234200000</div>
<div>H10 -0.0190100000 0.0047500000 -0.0185500000</div>
<div>H11 3.7834600000 -2.0785800000 0.0768300000</div>
<div>H12 -0.0477300000 0.0578100000 2.5026300000</div>
<div>H13 3.7465200000 -2.0206400000 2.5977800000</div>
<div>}</div>
<div>basis=desavdz-rev5</div>
<div>spherical</div>
<div>core,9</div>
<div>{df-hf,accu=15,maxit=100</div>
<div>}</div>
<div>{df-lmp2</div>
<div>local,thrbp=0.980,mergedom=1</div>
<div>pipek,delete=2,method=3</div>
<div>}</div>
<div>{optg,maxit=50</div>
<div>method,slrf</div>
<div>constraint,-0.226874,outofplane,atoms=[7,6,8,9]</div>
<div>}</div>
<div>put,xyz</div>
<div>jobstep opt0_w_basis_d</div>
<div><br>
<br>
</div>
</div>
</div>
</div>
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