Calculating spinorbit matrix elements

 Posts: 10
 Joined: 10 May 2016, 12:39
 First name(s): Qinghua
 Last name(s): Wu
 Affiliation: Anhui Normal University
 Country: China
Re: Calculating spinorbit matrix elements
Dear Olav,
Thank you for your reply! But in some literature they used the S1 or T1 optimized geometry to calculated SOC. It's there any distinctions?
Best regards!
Qinghua
Thank you for your reply! But in some literature they used the S1 or T1 optimized geometry to calculated SOC. It's there any distinctions?
Best regards!
Qinghua

 Posts: 519
 Joined: 15 Oct 2013, 05:37
 First name(s): Peter
 Middle name(s): Robert
 Last name(s): Taylor
 Affiliation: Aarhus University
 Country: Denmark
Re: Calculating spinorbit matrix elements
It is difficult to understand what you are asking. Obviously, if you run calculations at different geometries you will obtain different results for any property. Whether they will change much depends on the system and the property of interest. As an extreme example, you can calculate the dipole moment of HF, which near the minimum in the potential will be substantial. If you dissociate the molecule (with a wave function, such as MCSCF, that can describe this qualitatively correctly) you will obtain an H atom and an F atom and the dipole moment will be zero. (Actually, as a result of symmetrybreaking in the asymptotic limit this is not exactly true, but it is close enough.)
So what is it you want to calculate, and why? And what (say) experiments are you trying to compare with. I have lost count, if not yet patience, of my postings pleading with people to tell us what it is they are actually trying to calculate! As opposed to "some people do it this way, some people do it that way, what should I do"?!
Best regards
Pete
So what is it you want to calculate, and why? And what (say) experiments are you trying to compare with. I have lost count, if not yet patience, of my postings pleading with people to tell us what it is they are actually trying to calculate! As opposed to "some people do it this way, some people do it that way, what should I do"?!
Best regards
Pete

 Posts: 10
 Joined: 10 May 2016, 12:39
 First name(s): Qinghua
 Last name(s): Wu
 Affiliation: Anhui Normal University
 Country: China
Re: Calculating spinorbit matrix elements
Dear Pete,
Sorry to make you confuse. I am want to computing SOCs between higherlying singlet and triplet excited states. But in some literature, for example(Dyes and Pigments, 2016, 130, 9 and J. Org. Chem. 2015, 80, 5958−5963), they respectively using the S1 and T1 optimized geometry. This is what I feel confused.
Thank you very much and best regards!
Qinghua
Sorry to make you confuse. I am want to computing SOCs between higherlying singlet and triplet excited states. But in some literature, for example(Dyes and Pigments, 2016, 130, 9 and J. Org. Chem. 2015, 80, 5958−5963), they respectively using the S1 and T1 optimized geometry. This is what I feel confused.
Thank you very much and best regards!
Qinghua

 Posts: 519
 Joined: 15 Oct 2013, 05:37
 First name(s): Peter
 Middle name(s): Robert
 Last name(s): Taylor
 Affiliation: Aarhus University
 Country: Denmark
Re: Calculating spinorbit matrix elements
So if you use Dalton to calculate these sorts of properties you will run one calculation at a specific geometry. With such methodology it is not possible to calculate properties where e.g. S1 is at some calculated equilibrium geometry and T1 is at some different calculated equilibrium geometry. You need to ask yourself what is relevant for what you want to study. For example, if the ultimate interest were relaxation via phosphorescence to the ground state, most likely you would want to use the groundstate geometry. If your interest is relaxation of excited singlets to the lowest excited triplet (and no further) you might want to use excitedstate geometries. There is no "onesize" answer here  it depends, as I said in my previous posting, what it is you wish to compute. If I may editorialize further, it is not always wise to look at what previous authors have done. Much more important is to understand what (e.g.) experimentalists are doing, and what they need to help explain/interpret their experiments. But do not rely on experimentalists to tell you what they (think they) need to know! All too often experimentalists will say they need to know "this" because they do not believe, or are unaware, that we can calculate "that", which is what they really need. Understand their experiment, and if you can relate it properties that can be calculated, do those calculations.
Best regards
Pete
Best regards
Pete

 Posts: 10
 Joined: 10 May 2016, 12:39
 First name(s): Qinghua
 Last name(s): Wu
 Affiliation: Anhui Normal University
 Country: China
Re: Calculating spinorbit matrix elements
Dear Pete,
Many thanks to you for your help!
Thanks again and best regards!
Qinghua
Many thanks to you for your help!
Thanks again and best regards!
Qinghua

 Posts: 15
 Joined: 20 Sep 2016, 04:06
 First name(s): Folwe
 Last name(s): wang
 Affiliation: High University
 Country: China
Re: Calculating spinorbit matrix elements
Dear everyone:
I want to know how to calculate spinorbit coupling matrix element between ground state and triplet state.Where should I set it up？Which parameters should be changed?（I have carefully read input that calculates SOC between the single excited states and the triplet state ）
I want to know how to calculate spinorbit coupling matrix element between ground state and triplet state.Where should I set it up？Which parameters should be changed?（I have carefully read input that calculates SOC between the single excited states and the triplet state ）

 Posts: 256
 Joined: 27 Jun 2013, 18:44
 First name(s): Hans Jørgen
 Middle name(s): Aagaard
 Last name(s): Jensen
 Affiliation: Universith of Southern Denmark
 Country: Denmark
Re: Calculating spinorbit matrix elements
For BreitPauli spinorbit coupling (both one and twoelectron operators) between singlet ground state and triplet excited states at the MCSCF level, see the test
For AMFI meanfield spinorbit coupling, change the input keyword
 Hans Jørgen.
rsp_sreslrso
.For AMFI meanfield spinorbit coupling, change the input keyword
.SPINO
to .MNFSO
. Hans Jørgen.

 Posts: 15
 Joined: 20 Sep 2016, 04:06
 First name(s): Folwe
 Last name(s): wang
 Affiliation: High University
 Country: China
Re: Calculating spinorbit matrix elements
Dear hjaaj
Thank you fou your help. I, a tyro, calculate phosphorescent materials containing heay atoms(Iridium or Platinum). I have computed the example you recommended. But I do not know where the soc matrix element between ground state and triplet state of output is. Meanwhile, I have calculated one file about heay atom Iridium, but it can not end normally. I hope to get your help.(st_st4.out is recommended example, and s0t1_peng1.out is my molecule.)
Thanks and best wishes !
Thank you fou your help. I, a tyro, calculate phosphorescent materials containing heay atoms(Iridium or Platinum). I have computed the example you recommended. But I do not know where the soc matrix element between ground state and triplet state of output is. Meanwhile, I have calculated one file about heay atom Iridium, but it can not end normally. I hope to get your help.(st_st4.out is recommended example, and s0t1_peng1.out is my molecule.)
Thanks and best wishes !
 Attachments

 s0t1_peng1.out
 (148.36 KiB) Downloaded 125 times

 st_st4.out
 (59.42 KiB) Downloaded 128 times

 Posts: 519
 Joined: 15 Oct 2013, 05:37
 First name(s): Peter
 Middle name(s): Robert
 Last name(s): Taylor
 Affiliation: Aarhus University
 Country: Denmark
Re: Calculating spinorbit matrix elements
If you are interested in "phosphorescence" (by which I mean decay back to the ground state from a triplet state after intersystem crossing from a singlet state), Dalton can calculate this directly: this is documented in the manual. I am not sure why you want to calculate some spinorbit matrix elements directly?
Note that if you are calculating heavy elements and are using ECPs (it is not right now convenient for me to download your outputs so I cannot see them: that is a function of my situation and not in any way your fault!) you must, I am pretty sure, avoid the meanfield (AMFI) approach. If I recall correctly, Bernd Schimmelpfennig, who is expert in this area, has posted on this before. AMFI and ECPs are not designed to coexist, I think.
Best regards
Pete
Note that if you are calculating heavy elements and are using ECPs (it is not right now convenient for me to download your outputs so I cannot see them: that is a function of my situation and not in any way your fault!) you must, I am pretty sure, avoid the meanfield (AMFI) approach. If I recall correctly, Bernd Schimmelpfennig, who is expert in this area, has posted on this before. AMFI and ECPs are not designed to coexist, I think.
Best regards
Pete

 Posts: 15
 Joined: 20 Sep 2016, 04:06
 First name(s): Folwe
 Last name(s): wang
 Affiliation: High University
 Country: China
Re: Calculating spinorbit matrix elements
Dear Pete,
Thank you very much for your reply. I need to discuss two aspects of radiative and nonradiative transitions about Phosphorescent organic metal complexes. I want to discuss the elements ,such as transition dipole moment and matrix element, which influences radiative transition rate. I use the effectivecore oneelectron spinorbit operator method with ECP basis set to compute SOC matrix element between singlet excited states and triplet states, am I correct? If I am wrong, please correct me. Meanwhile, I need to discuss nonradiative transition that is affected by matrix element between ground state and lowest triplet state. So, I would like to calculate matrix element between ground state and lowest triplet state. I read the previous post and the output, but I do not know how to define SOC matrix element between the ground state and the triplet state. In recommended example that I test, I do not find where I want the data is. I need your help.
Thanks again and best regards!
xiaolin
Thank you very much for your reply. I need to discuss two aspects of radiative and nonradiative transitions about Phosphorescent organic metal complexes. I want to discuss the elements ,such as transition dipole moment and matrix element, which influences radiative transition rate. I use the effectivecore oneelectron spinorbit operator method with ECP basis set to compute SOC matrix element between singlet excited states and triplet states, am I correct? If I am wrong, please correct me. Meanwhile, I need to discuss nonradiative transition that is affected by matrix element between ground state and lowest triplet state. So, I would like to calculate matrix element between ground state and lowest triplet state. I read the previous post and the output, but I do not know how to define SOC matrix element between the ground state and the triplet state. In recommended example that I test, I do not find where I want the data is. I need your help.
Thanks again and best regards!
xiaolin

 Posts: 519
 Joined: 15 Oct 2013, 05:37
 First name(s): Peter
 Middle name(s): Robert
 Last name(s): Taylor
 Affiliation: Aarhus University
 Country: Denmark
Re: Calculating spinorbit matrix elements
I am not an expert in these sorts of calculations, but I am pretty sure, based on previous postings, more expert people like Bernd Schimmelpfennig or Olav Vahtras would say that it is not reasonable to use an effective spinorbit method like AMFI with conventional ECPs. Because the latter were parametrized without any reference to the former, and the chances are they will not work together. It is a bit like putting 89 octane fuel in a Formula 1 car: it may get you round the circuit, but the chances are you're not going to be very successful...
Calculating phosphorescence is documented in the manual: there is no reason to start worrying (in this particular context!) about radiative versus nonradiative transitions. For heavy elements, I think if you are using ECPs you have little alternative but to use the full spinorbit operator. As I said above, effective oneelectron operators like AMFI will not do.
Best regards
Pete
Calculating phosphorescence is documented in the manual: there is no reason to start worrying (in this particular context!) about radiative versus nonradiative transitions. For heavy elements, I think if you are using ECPs you have little alternative but to use the full spinorbit operator. As I said above, effective oneelectron operators like AMFI will not do.
Best regards
Pete

 Posts: 15
 Joined: 20 Sep 2016, 04:06
 First name(s): Folwe
 Last name(s): wang
 Affiliation: High University
 Country: China
Re: Calculating spinorbit matrix elements
Dear Pete
Than you for your advisement. I don't quite understand the spinorbit coupling operator, and I have a lack of quantitative knowledge. I calculate one molecule containing Iridium atom by three methods. I am not sure whether the full spinorbit operator use keyword .SPINORBIT. I hope to get the correct answer. If what you said I undstand wroing, can you tell me full spinorbit operator use which keyword? I have known my system possessing heay metal can not use AMFI poerator, because I find the result unreasonable. I find the result, computed by effective oneelectron operators with ECP basis set, order of magnitude is what I want. I also calculate the same molecule by .SPINORBIT keyword with ECP basis set, and the result order of magnitude is too small. I upload the outputs and inputs of two methods.
Thanks again and best regards!
xiaolin
Than you for your advisement. I don't quite understand the spinorbit coupling operator, and I have a lack of quantitative knowledge. I calculate one molecule containing Iridium atom by three methods. I am not sure whether the full spinorbit operator use keyword .SPINORBIT. I hope to get the correct answer. If what you said I undstand wroing, can you tell me full spinorbit operator use which keyword? I have known my system possessing heay metal can not use AMFI poerator, because I find the result unreasonable. I find the result, computed by effective oneelectron operators with ECP basis set, order of magnitude is what I want. I also calculate the same molecule by .SPINORBIT keyword with ECP basis set, and the result order of magnitude is too small. I upload the outputs and inputs of two methods.
Thanks again and best regards!
xiaolin
 Attachments

 peng1.mol
 (4.45 KiB) Downloaded 87 times

 full_peng1.out
 (160.64 KiB) Downloaded 101 times

 full.dal
 (219 Bytes) Downloaded 125 times

 effectiveCoreOneElectron_peng1.out
 (161.82 KiB) Downloaded 114 times

 effectiveCoreOneElectron.dal
 (207 Bytes) Downloaded 104 times
Re: Calculating spinorbit matrix elements
Please note that it only makes sense to use the full spinorbit operator if you also have an allelectron wave function (i.e. not ECPs). Of the two calculations you provide only the second makes sense (EffectiveCoreOneElectron). Even so, this is such a crude approximation that the best you can hope for is a result with the correct order of magnitude. The Ir atom has here an effective semiempirical charge of > 1000 to compensate for the lack of Ir core electrons in the wave function.
Regards,
Olav
Regards,
Olav

 Posts: 519
 Joined: 15 Oct 2013, 05:37
 First name(s): Peter
 Middle name(s): Robert
 Last name(s): Taylor
 Affiliation: Aarhus University
 Country: Denmark
Re: Calculating spinorbit matrix elements
This (Olav) certainly clarifies what I already thought had been posted about spinorbit and ECPs and heavy elements. But just out of interest (because I do very few finestructure calculations, and even fewer heavy elements) what is the best procedure for someone who (say) wants to do calculations of fine structure in a platinum complex? Can they do anything useful with Dalton? Or should we be telling them up front that we don't have the technology (which frankly, setting aside our sister code DIRAC...) means noone else has either!
Best regards
Pete
Best regards
Pete

 Posts: 15
 Joined: 20 Sep 2016, 04:06
 First name(s): Folwe
 Last name(s): wang
 Affiliation: High University
 Country: China
Re: Calculating spinorbit matrix elements
Dear Olav and Pete
Thank you very much for your advisement. I feel sorry for my late reply. I feel difficult to understand the meaning behind the words of posts due to the lack of quantitative knowledge. I will now read the instruction carefully and learn new knowledge.
Best regards
xiaolin
Thank you very much for your advisement. I feel sorry for my late reply. I feel difficult to understand the meaning behind the words of posts due to the lack of quantitative knowledge. I will now read the instruction carefully and learn new knowledge.
Best regards
xiaolin

 Posts: 15
 Joined: 20 Sep 2016, 04:06
 First name(s): Folwe
 Last name(s): wang
 Affiliation: High University
 Country: China
Re: Calculating spinorbit matrix elements
Dear everyone,
I have a question to consult with engineer and want to get your help. I need calculate the SOC matrix elemnet betweent ground and T1 state. I am not sure which configuration should be used in the input file. It will be greatly appreciated if I can get your kind help. Thank you.
Regards
xiaolin
I have a question to consult with engineer and want to get your help. I need calculate the SOC matrix elemnet betweent ground and T1 state. I am not sure which configuration should be used in the input file. It will be greatly appreciated if I can get your kind help. Thank you.
Regards
xiaolin

 Posts: 10
 Joined: 10 May 2016, 12:39
 First name(s): Qinghua
 Last name(s): Wu
 Affiliation: Anhui Normal University
 Country: China
Re: Calculating spinorbit matrix elements
Dear everyone，
I would like to calculate spinorbit matrix elements between excited states (S1 > Tn), by the quadraticresponse TDDFT approach, on systems containing heavy atoms. The SOC operator makes use of a semiempirical effective singleelectron approximation. The obtained results seems to be wrong. The attachment is the output. I also want to use BreitPauli method to calculate the spinorbit matrix elements. How should my input file be modified?
Thank you very much and best regards!
Qinghua
I would like to calculate spinorbit matrix elements between excited states (S1 > Tn), by the quadraticresponse TDDFT approach, on systems containing heavy atoms. The SOC operator makes use of a semiempirical effective singleelectron approximation. The obtained results seems to be wrong. The attachment is the output. I also want to use BreitPauli method to calculate the spinorbit matrix elements. How should my input file be modified?
Thank you very much and best regards!
Qinghua
 Attachments

 2ad.out
 (121.41 KiB) Downloaded 49 times

 Posts: 256
 Joined: 27 Jun 2013, 18:44
 First name(s): Hans Jørgen
 Middle name(s): Aagaard
 Last name(s): Jensen
 Affiliation: Universith of Southern Denmark
 Country: Denmark
Re: Calculating spinorbit matrix elements
Dear Qunghua
1. Please open a new thread for a new question!
2. Anyway, I have looked at your problem. Dalton detects that your molecule has C2 symmetry, and runs it in C2 symmetry which has two irreps.After the .ROOTS key word Dalton thus expects two numbers, telling how many roots you want in each symmetry. You only gave one number ("3"), this is the reason for the error exit. Alternatively you can request Dalton to run without symmetry with "Nosymmetry" the appropriate place in the .mol file, and then your .dal input is fine.
 Hans Jørgen.
1. Please open a new thread for a new question!
2. Anyway, I have looked at your problem. Dalton detects that your molecule has C2 symmetry, and runs it in C2 symmetry which has two irreps.After the .ROOTS key word Dalton thus expects two numbers, telling how many roots you want in each symmetry. You only gave one number ("3"), this is the reason for the error exit. Alternatively you can request Dalton to run without symmetry with "Nosymmetry" the appropriate place in the .mol file, and then your .dal input is fine.
 Hans Jørgen.
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