It will be centered for normal users. The reason why it looks not centered is because of the edit pencil next to the username for mods and admins. You can move that somewhere else on the template if you wish.
For postbit_legacy find
HTML Code:
<div class="username_container">
<vb:if condition="$post['userid']">
{vb:raw memberaction_dropdown}
{vb:raw post.onlinestatus}
<vb:else />
<span class="username guest">{vb:raw post.musername}</span>
</vb:if>
</div>
<span class="usertitle">
{vb:raw post.usertitle}
</span>
<vb:if condition="$post['rank']">
<span class="rank">{vb:raw post.rank}</span>
</vb:if>
{vb:raw template_hook.postbit_userinfo_left}
<vb:if condition="$show['reputation']">
<span class="postbit_reputation" id="repdisplay_{vb:raw post.postid}_{vb:raw post.userid}" title="{vb:raw post.username} {vb:raw post.level}">
<vb:each from="reputationdisplay" value="row">
<img class="{vb:raw row.class}" src="{vb:stylevar imgdir_reputation}/reputation_{vb:raw row.posneg}{vb:raw row.imgext}" alt="" />{vb:raw row.rowend}
</vb:each>
</span>
</vb:if>
Add <div style="text-align:center;"> </div> around the code above
Find
HTML Code:
<a class="postuseravatar" href="{vb:link member, {vb:raw post}}" title="{vb:rawphrase {vb:raw post['onlinestatusphrase']}, {vb:raw post.username}}">
Add style="float:none;text-align:center;" to this element