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<p>Hi, dear geroge,</p>
<p><br>
</p>
<p>T<span style="font-size: 12pt;">o force the potential </span><span style="font-size: 12pt;">to decay to zero, it must be uniformly shifted </span><span style="font-size: 12pt;">by the corresponding asymptotic value (R = 50 Ang).</span></p>
<p><span style="font-size: 12pt;"><br>
</span></p>
<p><span style="font-size: 12pt;">Best regards, </span></p>
<p><span style="font-size: 12pt;">Bop</span></p>
</div>
<hr style="display:inline-block;width:98%" tabindex="-1">
<div id="divRplyFwdMsg" dir="ltr"><font face="Calibri, sans-serif" style="font-size:11pt" color="#000000"><b>De :</b> Molpro-user <molpro-user-bounces@molpro.net> de la part de george <george.iitm@gmail.com><br>
<b>Envoyé :</b> jeudi 15 décembre 2016 16:44:34<br>
<b>À :</b> molpro-user molpro-user<br>
<b>Objet :</b> [molpro-user] About Size consistent problem in O2H+</font>
<div> </div>
</div>
<div>
<div dir="ltr">Dear users
<div><br>
</div>
<div><br>
</div>
<div>I am calculating CBS PES of O2H+ ion. When I calculate a single point calculation of X-state keeping the distance between OH+ fragment and O-atom at 50 Ang at CAS/cc-pVQZ level, I get the following energy at CAS level E_cas = -149.8371634 hartrees.</div>
<div><br>
</div>
<div>Now, I do the individual calculation at the same level of the OH+ ion and O-atom seperately and I get E_cas(OH+) = -75.02897195 hartrees and E_cas(O) = -74.80987715 hartrees. When I sum, I get E_cas(OH+ and O) = -149.83884910 hartrees. I find that the
summed energy and energy of the O2H+ ion calculated at 50 Ang differ by 0.0016857 hartrees which is sizable according to my opinion. </div>
<div><br>
</div>
<div>My question is that if there is any way out to reduce this difference to almost zero hartrees (i.e to say about 0.000001 hartrees)</div>
<div><br>
</div>
<div>I write below input file I used for each of the above mentioned calculation for the users to find out the possible mistakes in them if any</div>
<div><br>
</div>
<div>I will be happy to receive any comments from the experienced users to this issue.</div>
<div><br>
</div>
<div>Input file for O2H+ ion at 50 Ang</div>
<div>-----------------------------------------------</div>
<span style="font-family:monospace"><span style="color:rgb(0,0,0)"> ***,o2hp </span>
<br>
print,orbitals,civector <br>
!file,1,<a href="http://o2hp_ci_cs_2_1_titan.int">o2hp_ci_cs_2_1_titan.int</a>
<br>
file,2,b.wfu <br>
!symmetry,x
<br>
<br>
rcm=[1.258030346,0.9,1,1.1,1.15,1.2,1.25,1.3,1.35,1.4,1.5,1.6,1.7,1.8,1.9,2.0,2.05,2.1,2.2,2.3,2.4,2.6,2.8,\
<br>
3,3.2,3.4,3.6,3.8,4,4.5,5,6,8,10,15,20,30,50] ANG <br>
<br>
roh=1.008682076 ANG <br>
theta=30 DEGREE <br>
<br>
basis=cc-pVQZ <br>
<br>
do i=1,#rcm <br>
<br>
ro=rcm(i) <br>
<br>
symmetry,x <br>
geometry={ !geometry specification, using z-matrix
<br>
3 <br>
O2HP <br>
O 0 0 -(1/17)*roh <br>
H 0 0 (16/17)*roh <br>
O 0 ro*sin(theta) ro*cos(theta) <br>
} <br>
<br>
<br>
{multi;config;wf,16,2,2;state,5;dm} <br>
emulti_gs(i)=energy(1) <br>
emulti_1xs(i)=energy(2) <br>
emulti_2xs(i)=energy(3) <br>
emulti_3xs(i)=energy(4) <br>
emulti_4xs(i)=energy(5) <br>
{ci;option,maxiti=5000;wf,16,2,2;state,5} <br>
eci_gs(i)=energy(1) <br>
eci_1xs(i)=energy(2) <br>
eci_2xs(i)=energy(3) <br>
eci_3xs(i)=energy(4) <br>
eci_4xs(i)=energy(5)<br>
</span><span style="font-family:monospace"><span style="color:rgb(0,0,0)"><br>
</span></span>
<div><span style="font-family:monospace"><span style="color:rgb(0,0,0)">table,rcm,emulti_gs,emulti_1xs,emulti_2xs,emulti_3xs,emulti_4xs
</span><br>
Title,Results for O2H+ <br>
table,rcm,eci_gs,eci_1xs,eci_2xs,eci_3xs,eci_4xs <br>
<br>
end do <br>
<br>
{pop;individual;density,2140.2,charge,state=1.2} <br>
{pop;individual;density,2140.2,charge,state=2.2} <br>
{pop;individual;density,2140.2,charge,state=3.2} <br>
{pop;individual;density,2140.2,charge,state=4.2} <br>
{pop;individual;density,2140.2,charge,state=5.2}<br>
<br>
</span>
<div> Input file for OH+ fragment</div>
<div>-------------------------------------------</div>
<div><span style="font-family:monospace"><span style="color:rgb(175,95,0)">***</span><span style="color:rgb(0,0,0)">,o2h</span><span style="color:rgb(175,95,0)">+</span><span style="color:rgb(0,0,0)">
</span><br>
<span style="color:rgb(175,95,0)">print</span><span style="color:rgb(0,0,0)">,orbitals,civector
</span><br>
file,<span style="color:rgb(178,24,24)">1</span><span style="color:rgb(0,0,0)">,oh</span><span style="color:rgb(175,95,0)">+</span><span style="color:rgb(0,0,0)">_ci_c2v_4_1_mar5</span><span style="color:rgb(178,24,178)">.</span><span style="color:rgb(0,0,0)">int
</span><br>
file,<span style="color:rgb(178,24,24)">2</span><span style="color:rgb(0,0,0)">,oh</span><span style="color:rgb(175,95,0)">+</span><span style="color:rgb(0,0,0)">_ci_c2v_4_1_mar5</span><span style="color:rgb(178,24,178)">.</span><span style="color:rgb(0,0,0)">wfu
</span><br>
<br>
!rcm<span style="color:rgb(175,95,0)">=</span><span style="color:rgb(178,24,178)">[</span><span style="color:rgb(178,24,24)">1</span><span style="color:rgb(178,24,178)">.</span><span style="color:rgb(178,24,24)">0275782448</span><span style="color:rgb(0,0,0)">,</span><span style="color:rgb(178,24,24)">0</span><span style="color:rgb(178,24,178)">.</span><span style="color:rgb(178,24,24)">5</span><span style="color:rgb(0,0,0)">,</span><span style="color:rgb(178,24,24)">0</span><span style="color:rgb(178,24,178)">.</span><span style="color:rgb(178,24,24)">55</span><span style="color:rgb(0,0,0)">,</span><span style="color:rgb(178,24,24)">0</span><span style="color:rgb(178,24,178)">.</span><span style="color:rgb(178,24,24)">6</span><span style="color:rgb(0,0,0)">,</span><span style="color:rgb(178,24,24)">0</span><span style="color:rgb(178,24,178)">.</span><span style="color:rgb(178,24,24)">65</span><span style="color:rgb(0,0,0)">,</span><span style="color:rgb(178,24,24)">0</span><span style="color:rgb(178,24,178)">.</span><span style="color:rgb(178,24,24)">7</span><span style="color:rgb(0,0,0)">,</span><span style="color:rgb(178,24,24)">0</span><span style="color:rgb(178,24,178)">.</span><span style="color:rgb(178,24,24)">75</span><span style="color:rgb(0,0,0)">,</span><span style="color:rgb(178,24,24)">0</span><span style="color:rgb(178,24,178)">.</span><span style="color:rgb(178,24,24)">8</span><span style="color:rgb(0,0,0)">,</span><span style="color:rgb(178,24,24)">0</span><span style="color:rgb(178,24,178)">.</span><span style="color:rgb(178,24,24)">85</span><span style="color:rgb(0,0,0)">,</span><span style="color:rgb(178,24,24)">0</span><span style="color:rgb(178,24,178)">.</span><span style="color:rgb(178,24,24)">9</span><span style="color:rgb(0,0,0)">,</span><span style="color:rgb(178,24,24)">0</span><span style="color:rgb(178,24,178)">.</span><span style="color:rgb(178,24,24)">925</span><span style="color:rgb(0,0,0)">,</span><span style="color:rgb(178,24,24)">0</span><span style="color:rgb(178,24,178)">.</span><span style="color:rgb(178,24,24)">95</span><span style="color:rgb(0,0,0)">,</span><span style="color:rgb(178,24,24)">0</span><span style="color:rgb(178,24,178)">.</span><span style="color:rgb(178,24,24)">975</span><span style="color:rgb(0,0,0)">,</span><span style="color:rgb(178,24,24)">1</span><span style="color:rgb(0,0,0)">,</span><span style="color:rgb(178,24,24)">1</span><span style="color:rgb(178,24,178)">.</span><span style="color:rgb(178,24,24)">025</span><span style="color:rgb(0,0,0)">,</span><span style="color:rgb(178,24,24)">1</span><span style="color:rgb(178,24,178)">.</span><span style="color:rgb(178,24,24)">05</span><span style="color:rgb(0,0,0)">,</span><span style="color:rgb(178,24,24)">1</span><span style="color:rgb(178,24,178)">.</span><span style="color:rgb(178,24,24)">075</span><span style="color:rgb(0,0,0)">,</span><span style="color:rgb(178,24,24)">1</span><span style="color:rgb(178,24,178)">.</span><span style="color:rgb(178,24,24)">1</span><span style="color:rgb(0,0,0)">,</span><span style="color:rgb(178,24,24)">1</span><span style="color:rgb(178,24,178)">.</span><span style="color:rgb(178,24,24)">15</span><span style="color:rgb(0,0,0)">,</span><span style="color:rgb(178,24,24)">1</span><span style="color:rgb(178,24,178)">.</span><span style="color:rgb(178,24,24)">2</span><span style="color:rgb(0,0,0)">,</span><span style="color:rgb(178,24,24)">1</span><span style="color:rgb(178,24,178)">.</span><span style="color:rgb(178,24,24)">4</span><span style="color:rgb(0,0,0)">,</span><span style="color:rgb(178,24,24)">1</span><span style="color:rgb(178,24,178)">.</span><span style="color:rgb(178,24,24)">6</span><span style="color:rgb(0,0,0)">,\
</span><br>
! <span style="color:rgb(178,24,24)">1</span><span style="color:rgb(178,24,178)">.</span><span style="color:rgb(178,24,24)">8</span><span style="color:rgb(0,0,0)">,</span><span style="color:rgb(178,24,24)">2</span><span style="color:rgb(0,0,0)">,</span><span style="color:rgb(178,24,24)">2</span><span style="color:rgb(178,24,178)">.</span><span style="color:rgb(178,24,24)">5</span><span style="color:rgb(0,0,0)">,</span><span style="color:rgb(178,24,24)">3</span><span style="color:rgb(0,0,0)">,</span><span style="color:rgb(178,24,24)">3</span><span style="color:rgb(178,24,178)">.</span><span style="color:rgb(178,24,24)">5</span><span style="color:rgb(0,0,0)">,</span><span style="color:rgb(178,24,24)">4</span><span style="color:rgb(0,0,0)">,</span><span style="color:rgb(178,24,24)">4</span><span style="color:rgb(178,24,178)">.</span><span style="color:rgb(178,24,24)">5</span><span style="color:rgb(0,0,0)">,</span><span style="color:rgb(178,24,24)">5</span><span style="color:rgb(0,0,0)">,</span><span style="color:rgb(178,24,24)">6</span><span style="color:rgb(0,0,0)">,</span><span style="color:rgb(178,24,24)">8</span><span style="color:rgb(0,0,0)">,</span><span style="color:rgb(178,24,24)">10</span><span style="color:rgb(0,0,0)">,</span><span style="color:rgb(178,24,24)">12</span><span style="color:rgb(0,0,0)">,</span><span style="color:rgb(178,24,24)">14</span><span style="color:rgb(0,0,0)">,</span><span style="color:rgb(178,24,24)">16</span><span style="color:rgb(0,0,0)">,</span><span style="color:rgb(178,24,24)">18</span><span style="color:rgb(0,0,0)">,</span><span style="color:rgb(178,24,24)">20</span><span style="color:rgb(178,24,178)">]</span><span style="color:rgb(0,0,0)">
ANG </span><br>
rcm<span style="color:rgb(175,95,0)">=</span><span style="color:rgb(178,24,178)">[</span><span style="color:rgb(178,24,24)">1</span><span style="color:rgb(178,24,178)">.</span><span style="color:rgb(178,24,24)">008682076</span><span style="color:rgb(178,24,178)">]</span><span style="color:rgb(0,0,0)">
ANG </span><br>
<br>
geometry<span style="color:rgb(175,95,0)">=</span><span style="color:rgb(0,0,0)">{ !geometry specification, using z-matrix
</span><br>
o <br>
h o roh <br>
} <br>
<br>
basis<span style="color:rgb(175,95,0)">=cc</span><span style="color:rgb(0,0,0)">-pVQZ
</span><br>
<br>
do i<span style="color:rgb(175,95,0)">=</span><span style="color:rgb(178,24,24)">1</span><span style="color:rgb(0,0,0)">,#rcm
</span><br>
<br>
roh<span style="color:rgb(175,95,0)">=</span><span style="color:rgb(0,0,0)">rcm</span><span style="color:rgb(178,24,178)">(</span><span style="color:rgb(0,0,0)">i</span><span style="color:rgb(178,24,178)">)</span><span style="color:rgb(0,0,0)">
</span><br>
<br>
{multi<span style="color:rgb(178,24,178)">;</span><span style="color:rgb(0,0,0)">config</span><span style="color:rgb(178,24,178)">;</span><span style="color:rgb(0,0,0)">wf,</span><span style="color:rgb(178,24,24)">8</span><span style="color:rgb(0,0,0)">,</span><span style="color:rgb(178,24,24)">4</span><span style="color:rgb(0,0,0)">,</span><span style="color:rgb(178,24,24)">2</span><span style="color:rgb(178,24,178)">;</span><span style="color:rgb(0,0,0)">dm}
</span><br>
emulti_gs<span style="color:rgb(178,24,178)">(</span><span style="color:rgb(0,0,0)">i</span><span style="color:rgb(178,24,178)">)</span><span style="color:rgb(175,95,0)">=</span><span style="color:rgb(0,0,0)">energy</span><span style="color:rgb(178,24,178)">(</span><span style="color:rgb(178,24,24)">1</span><span style="color:rgb(178,24,178)">)</span><span style="color:rgb(0,0,0)">
</span><br>
ci <br>
eci_gs<span style="color:rgb(178,24,178)">(</span><span style="color:rgb(0,0,0)">i</span><span style="color:rgb(178,24,178)">)</span><span style="color:rgb(175,95,0)">=</span><span style="color:rgb(0,0,0)">energy</span><span style="color:rgb(178,24,178)">(</span><span style="color:rgb(178,24,24)">1</span><span style="color:rgb(178,24,178)">)</span><span style="color:rgb(0,0,0)">
</span><br>
eci_gs_david<span style="color:rgb(178,24,178)">(</span><span style="color:rgb(0,0,0)">i</span><span style="color:rgb(178,24,178)">)</span><span style="color:rgb(175,95,0)">=</span><span style="color:rgb(0,0,0)">energd</span><span style="color:rgb(178,24,178)">(</span><span style="color:rgb(178,24,24)">1</span><span style="color:rgb(178,24,178)">)</span><span style="color:rgb(0,0,0)">
</span><br>
<br>
<span style="color:rgb(175,95,0)">end</span><span style="color:rgb(0,0,0)"> do </span>
<br>
<br>
table,rcm,emulti_gs,eci_gs,eci_gs_david <br>
Title,Results <span style="color:rgb(175,95,0)">for</span><span style="color:rgb(0,0,0)"> OH</span><span style="color:rgb(175,95,0)">+</span><span style="color:rgb(0,0,0)"> dissociation
</span><span style="color:rgb(178,24,24)">3</span><span style="color:rgb(0,0,0)">Sig- state
</span><br>
<br>
{pop<span style="color:rgb(178,24,178)">;</span><span style="color:rgb(0,0,0)">individual</span><span style="color:rgb(178,24,178)">;</span><span style="color:rgb(0,0,0)">density,</span><span style="color:rgb(178,24,24)">2140</span><span style="color:rgb(178,24,178)">.</span><span style="color:rgb(178,24,24)">2</span><span style="color:rgb(0,0,0)">,charge,state</span><span style="color:rgb(175,95,0)">=</span><span style="color:rgb(178,24,24)">1</span><span style="color:rgb(178,24,178)">.</span><span style="color:rgb(178,24,24)">4</span><span style="color:rgb(0,0,0)">}</span><br>
<br>
</span></div>
<div>Input file for O-atom</div>
</div>
<div>----------------------------------</div>
<div><span style="font-family:monospace"><span style="color:rgb(175,95,0)">***</span><span style="color:rgb(0,0,0)">,o
</span><br>
<span style="color:rgb(175,95,0)">print</span><span style="color:rgb(0,0,0)">,orbitals,civector
</span><br>
<br>
geometry<span style="color:rgb(175,95,0)">=</span><span style="color:rgb(0,0,0)">{ !geometry specification, using z-matrix
</span><br>
o <br>
} <br>
<br>
basis<span style="color:rgb(175,95,0)">=cc</span><span style="color:rgb(0,0,0)">-pVQZ
</span><br>
<br>
<br>
{multi<span style="color:rgb(178,24,178)">;</span><span style="color:rgb(0,0,0)">wf,</span><span style="color:rgb(178,24,24)">8</span><span style="color:rgb(0,0,0)">,</span><span style="color:rgb(178,24,24)">4</span><span style="color:rgb(0,0,0)">,</span><span style="color:rgb(178,24,24)">2</span><span style="color:rgb(178,24,178)">;</span><span style="color:rgb(0,0,0)">dm}
</span><br>
ci<br>
<br>
</span></div>
</div>
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